Long-workability calcium aluminate cement with hardening promoted by a temperature increase, and related use

ABSTRACT

Disclosed is to a calcium aluminate cement, including a calcium aluminate with a first crystallised mineralogical phase of calcium dialuminate CA2 including one calcium oxide CaO for two aluminium oxides Al 2 O 3  and/or a second crystallised mineralogical phase of dicalcium alumina silicate C2AS including two calcium oxides CaO for one aluminium oxide Al 2 O 3  and one silicon dioxide SiO 2 . The mass fraction of all of the first and second mineralogical phases in the calcium aluminate is greater than or equal to 80%.

TECHNICAL FIELD TO WHICH THE INVENTION RELATES

This invention generally relates to the field of cements of which thehardening in the presence of water is favoured by an increase intemperature.

It relates in particular to a calcium aluminate cement comprising acalcium aluminate with a first crystallised mineralogical phase ofcalcium dialuminate CA2 comprising one calcium oxide CaO for twoaluminium oxides Al₂O₃ and/or a second crystallised mineralogical phaseof dicalcium alumina silicate C2AS comprising two calcium oxides CaO forone aluminium oxide Al₂O₃ and one silicon dioxide SiO₂.

It also relates to a cementitious composition comprising such a calciumaluminate cement, mixed with water and possibly with other compoundssuch as fly ash, a granulated blast furnace slag, a silica flour, silicafume, metakaolin, quartz, fine limestone, sand, and adjuvants.

The invention has a particularly advantageous application in anyapplication where an increase in temperature is required or endured,such as for example the consolidating of oil wells.

TECHNOLOGICAL BACKGROUND

A cement is a mineral powder designed to be mixed with water in order toform a cementitious composition with a pasty or liquid consistency thathardens in order to form a hardened final material.

There are many cements on the market that can be distinguished, on theone hand, by their reactive properties with water, and on the otherhand, by the mechanical and chemical properties of the hardened finalmaterials that can be obtained from them.

For example, calcium aluminate cements provide the hardened finalmaterials with specific chemical properties of high resistance to acidcorrosion and mechanical properties of high resistance to hightemperatures and pressures.

The reactive properties of a cement when it is mixed with waterdetermine the workability of

the cementitious composition formed by the mixture of this cement withwater, i.e. the duration, also called “open time”, during which thiscementitious composition has a viscosity adapted to its use, namely, forexample, a low viscosity in order to allow the injection thereof intocracks, or a moderate viscosity in order to allow for the shapingthereof in formworks.

These reactive properties also determine the hardening kinetics of thecementitious composition during later phases of the reaction of thecement with the water. These are in particular the characteristics ofthe hydraulic setting of the cementitious composition, with thehydraulic setting being an accelerated exothermic phase of the hydrationreaction of the cement by the water, and of the speed at which the finalhardening of the material occurs after the hydraulic setting, namely inhow much time the hardened final material reaches a desired mechanicalresistance.

Furthermore, it is known that a relatively high temperature, i.e.greater than about 50° C., even greater than 30° C., can accelerate thehardening kinetics of a cementitious composition, and substantiallyreduce its workability in particular by favouring the thickening of thecementitious composition and by triggering the hydraulic setting faster.

In order to decrease the effect of the temperature on the reactivity ofthe cementitious compositions, it is common to add adjuvants to thecementitious compositions, such as setting retarders.

However, as several retarders can be used in the same cementitiouscomposition, these retarders can interact together and/or with the otheradditives of the cementitious composition, and it then becomes difficultto predict the hardening kinetics of this cementitious composition.

In addition, the presence of a retarder in the cementitious compositioncan lead to a lowering of the mechanical resistance of the hardenedfinal material.

Moreover, it is also known that, due to these problems of workabilityand of hardening kinetics, cementitious compositions with a calciumaluminate base are generally manufactured on site, i.e. the water isadded to the cement directly on the location of use of the cementitiouscompositions.

It is as such a regular occurrence that, on site, cementitiouscompositions with a base of calcium aluminate cements are prepared inproduction lines that are normally used to prepare cementitiouscompositions with a base of Portland cement.

As production lines comprise dead zones that are difficult to purgeand/or to clean, a small amount of cement may remain from one productioncampaign to another. As such, during the preparation of a cementitiouscomposition with a Portland cement base, it occurs that this Portlandcement has been polluted by remainders of calcium aluminate cement, orinversely.

Yet, Portland cements and calcium aluminate cements interact with eachother, and this interaction accelerates the hardening kinetics of thecementitious compositions obtained. As such, the hydraulic setting of acementitious composition with a base of a mixture of Portland cement andof calcium aluminate cement is initiated earlier than what is expectedfor a cementitious composition with a base of Portland cement or ofcalcium aluminate cement only. When this mixture results from aninvoluntary pollution, the acceleration in the setting can result inblocking the installations, which is very problematic.

An application wherein generally high temperatures are involved, and forwhich it is essential to control the workability and the hardeningkinetics of the cementitious compositions formed is the consolidating ofdrilling wells.

Drilling wells, and in particular oil wells, is a complex process thatconsists mainly in drilling the rock while introducing therein a tubularmetal body.

It is known to cement the walls of drilling wells in order to reinforcethe formwork of these wells and to protect the tubular body that isinserted therein from corrosion, as well as to seal this tubular body inthe neighbouring rock.

To do this, industrialists use cementitious compositions in the form ofaqueous suspensions commonly referred to as slurry, mainly comprising acement, possibly aggregates or specific cementitious additions,dispersed in a relatively large quantity of water, that they inject intothe tubular body to the bottom of the latter. The aqueous suspensionthen rises to the surface, in the space that exists between the rockwall and the tubular body.

It is then understood that the workability of the aqueous suspensionmust be such that this aqueous suspension can be injected to the bottomof the tubular body, and that the hydraulic setting of the aqueoussuspension must occur at a controlled moment after the rising to thesurface of this aqueous suspension, and this taking the undergroundconditions of high temperatures and pressures into account.

It is known for example from document US20130299170 complex cementitiouscompositions in the form of aqueous suspensions, suited for theconsolidating of oil drilling wells, that include calcium aluminatecements and setting retarders comprising an organic acid and a mixtureof polymers.

It is also known from documents U.S. Pat. No. 6,143,069 andUS20040255822 cementitious compositions in the form of an aqueoussuspension with a low density, suited for the consolidating of oildrilling wells, comprising a commercial calcium aluminate, of the brandSECAR60™ or REFCON™, fly ash, water, retarders such as citric, gluconicor tartaric acids and other additives such as foaming agents and agentsthat prevent the loss of fluid.

However, the cementitious compositions formulated as such to reduce theeffect of the temperature on their workability and their hardeningkinetics are particularly complex. They moreover result in the use ofmany different chemical compounds, which can have a harmful effect onthe environment.

There is therefore a need to be able to benefit from the propertiesprovided by the hydration of calcium aluminates while still more easilycontrolling the period of workability in particular when the temperatureis high, and tolerating a certain pollution by Portland cements or inPortland cements.

OBJECT OF THE INVENTION

In order to overcome the aforementioned disadvantages of prior art, thisinvention proposes a new calcium aluminate cement, that has theadvantageous properties of chemical resistance and of mechanicalresistance of this type of cement, as well as a naturally long open timewithout adding retarder, and even in the case of an involuntary mixturewith Portland cements.

More particularly, according to the invention a calcium aluminate cementis proposed such as described in the introduction, wherein the massfraction of all of said first and second mineralogical phases in saidcalcium aluminate is greater than or equal to 80%.

As such, thanks to these crystallised mineralogical phases, the calciumaluminate cement according to the invention has a controlled hardeningkinetics, without having to add a retarder.

More precisely, the Applicant observed that the calcium aluminatecements that comprise these mineralogical phases have, at ambienttemperature, an extremely long workability, and that the reactivity ofthese phases with water was favoured by an increase in temperature. Assuch, at ambient temperature, the reactivity of the calcium aluminatecement according to the invention with water is low and the kinetics ofthe hydration reaction is very slow. The workability of the cementitiouscomposition with a base of this cement is therefore controlled withoutadding setting retarders in the form of additional chemical compounds.

Furthermore, the hardening kinetics is controlled as the hydraulicsetting can be triggered and/or accelerated by an increase intemperature.

In addition, these mineralogical phases guarantee the calcium aluminatecement according to the invention with reduced interactions withPortland cements, which reduces the problems linked with thecross-contamination between Portland cements and calcium aluminatecements.

Finally, the calcium aluminate cement according to the invention hasproperties of mechanical resistance to high temperatures and to highpressures, and of chemical resistance to corrosion to acids similar tothose of calcium aluminate cements already known in prior art.

Other non-limiting and advantageous characteristics of the calciumaluminate cement in accordance with the invention, taken individually oraccording to any technically permissible combination, are as follows:

-   -   said calcium aluminate also comprises an amorphous portion, of        which the mass fraction in said calcium aluminate is less than        or equal to 20%;    -   said calcium aluminate further comprises a third crystallised        mineralogical phase of monocalcium aluminate CA comprising one        calcium oxide CaO (noted as C according to cement-manufacturer        notation) for one aluminium oxide Al₂O₃ (noted as A according to        cement-manufacturer notation) and/or a fourth crystallised        mineralogical phase of hexacalcium aluminate CA6 comprising one        calcium oxide CaO for six aluminium oxides Al₂O₃, the mass        fraction of all of the third and fourth mineralogical phases in        said calcium aluminate being less than or equal to 20%;    -   said calcium aluminate further comprises an additional        mineralogical phase of sulfocalcium aluminate C4A3$ comprising        four calcium oxides CaO for three aluminium oxides Al₂O₃ and one        sulphur oxide SO₃ (noted as $ according to cement-manufacturer        notation);    -   it comprises, by weight with respect to the total weight of said        calcium aluminate: 0% to 5% of an iron oxide Fe₂O₃, 0% to 5% of        a titanium oxide TiO₂, 0% to 5% of a sulphur oxide SO₃, 0% to 5%        of a magnesium oxide MgO, 0% to 2% of alkaline compounds;    -   it has the form of a powder that has a Blaine specific surface        area measured according to standard NF-EN-196-6 ranging between        2200 square centimetres per gram and 4500 square centimetres per        gram, preferably between 2900 and 3900 square centimetres per        gram;    -   it comprises, by weight with respect to the total weight of said        calcium aluminate: 50% to 60% of first crystallised        mineralogical phase CA2, 26% to 32% of second crystallised        mineralogical phase C2AS (S designating the silica SiO₂        according to cement-manufacturer notation), 2.5% to 3.5% of        third crystallised mineralogical phase CA, 0.5% to 1.5% of a        fifth crystallised mineralogical phase of tetracalcium        ferro-aluminate C4AF (F designating the iron oxide Fe₂O₃        according to cement-manufacturer notation), 10% to 15% of        additional crystallised mineralogical phases;    -   the calcium aluminate cement according to the invention        comprises from 0.5% to 15% of additional mineralogical phase of        sulfocalcium aluminate C4A3$, by weight with respect to the        total weight of said calcium aluminate.

The invention also proposes a cementitious composition comprising atleast the calcium aluminate cement according to the invention mixed withwater, and possibly cementitious additions such as fly ash and/or agranulated blast furnace slag and/or a silica flour and/or silica fumeand/or metakaolin, granulates such as quartz and/or fine limestoneand/or sand, and adjuvants.

The invention also proposes a use of the calcium aluminate cement suchas described hereinabove, according to which

a) a cementitious composition is realised by mixing at least saidcalcium aluminate cement with water,

b) said cementitious composition is set in place,

c) said cementitious composition is heated to a temperature rangingbetween 50° C. and 300° C., preferably between 80° C. and 280° C., insuch a way as to favour the setting of the cementitious composition.

The cementitious composition can further comprise aggregates (forexample sand) and/or adjuvants (for example retarders, accelerators orother) known to those skilled in the art.

In the temperature conditions of the step c), the pressure ispreferentially chosen to be high, i.e. greater than or equal tosaturation vapour pressure, in such a way that the water is present inliquid form or at least in the form of saturation vapour.

In particular, this use of the calcium aluminate cement has aparticularly advantageous application in consolidating drilling wells,and in particular oil drilling wells.

For this, in step a) of the use according to the invention, thecementitious composition is in the form of an aqueous suspension, and instep b), the cementitious composition is placed in an oil drilling well.

DETAILED DESCRIPTION OF AN EMBODIMENT

The following description with regards to the annexed drawings, providedas non-limiting examples, shall explain what the invention consists ofand how it can be realised.

In the annexed drawings:

FIG. 1 is a ternary lime-alumina-silica diagram, represented in massfraction of lime, alumina and silica;

FIG. 2 is a zoom of FIG. 1 in the area of interest [II-II] in order todescribe the range of composition of the calcium aluminate according tothe invention.

In the invention, and unless specified otherwise, the indication of aninterval of values “X to Y” or “between X and Y”, in this invention, isto be understood as including the values X and Y.

This invention relates to a calcium aluminate cement adapted to be mixedwith water in order to form a cementitious composition of which theworkability is naturally long, and of which the reactivity is favouredby an increase in temperature.

In the rest of the description, the term “cement” shall designate apowder designed to be mixed with water in order to form a cementitiouscomposition that is able to harden in order to form a hard finalmaterial.

The term “cementitious composition” shall designate the mixture of thecement with water and possibly with other additional compounds.

Finally, as shall be explained well in what follows, the “reactivity” orthe “reactive properties” of the cement characterise the capacity ofthis cement to react with water.

From a chemical point of view, the calcium aluminate cement according tothe invention comprises at least one calcium aluminate, i.e. a compoundcomprising both calcium oxide and aluminium oxide.

More precisely, here, the calcium aluminate of the cement according tothe invention comprises calcium oxide commonly referred to as lime CaO,aluminium oxide commonly referred to as alumina Al₂O₃, and silicondioxide commonly referred to as silica SiO₂.

In such a way as to lighten the notations, as is conventionally done bycement-manufacturers in their notations, we shall shorten in whatfollows lime CaO by the letter C, alumina Al₂O₃ by the letter A andsilica SiO₂ by the letter S.

These three compounds, namely lime C, alumina A and silica S, constitutethe majority compounds present in the calcium aluminate according to theinvention.

The calcium aluminate according to the invention can also comprise, byweight with respect to the total weight of said calcium aluminate:

-   -   0% to 5% of an iron oxide Fe₂O₃ (shortened to F according to        cement-manufacturer notation),    -   0% to 5% of a titanium oxide TiO₂ (shortened to T according to        cement-manufacturer notation),    -   0% to 5% of a sulphur oxide SO₃ (shortened to $ according to        cement-manufacturer notation),    -   0% to 5% of a magnesium oxide MgO (shortened to M according to        cement-manufacturer notation),    -   0% to 2% of alkaline compounds.

These other compounds are minority compounds of the calcium aluminate ofthe cement according to the invention. They constitute impurities thatgenerally come from raw materials used for the manufacture of thecalcium aluminate.

From a mineralogical point of view, the calcium aluminate cementaccording to the invention comprises a crystalline portion and anamorphous portion.

These crystalline and amorphous portions characterise the microscopicstate of the calcium aluminate cement according to the invention: thecrystalline portion of this calcium aluminate cement comprises atomsand/or molecules ordered according to a particular geometry, incrystallised mineralogical phases, while the amorphous portion of thiscalcium aluminate cement comprises atoms and/or molecules that arearranged in a disorderly manner in relation to one another, i.e. withoutany particular order.

Here, the calcium aluminate of the cement according to the invention isprimarily crystalline.

More precisely, advantageously, in the calcium aluminate cementaccording to the invention, the mass fraction of said crystallineportion in said calcium aluminate is greater than or equal to 80%.

In other words, the mass of the crystalline portion in relation to thetotal weight of the calcium aluminate of the cement according to theinvention, is greater than or equal to 80%.

As such, in the calcium aluminate cement according to the invention, themass fraction of the amorphous portion is less than or equal to 20%.

The crystalline portion has crystallised mineralogical phases which makeit possible to more specifically describe the calcium aluminate of thecement according to the invention.

Indeed, the quantity and the nature of the crystallised mineralogicalphases present in the cement according to the invention account for thechemical composition of said calcium aluminate.

In the rest of the description, these “crystallised mineralogicalphases” shall sometimes be referred to as “mineralogical phases”.

Here in particular, the crystallised mineralogical phases describe boththe structure on the atomic scale and the chemical composition of thecalcium aluminate, insofar they involve several different compounds.

In particular, here, the mineralogical phases of the calcium aluminateof the cement according to the invention involve lime C, alumina A andsilica S.

Generally, the crystallised mineralogical phases of calcium aluminatesare numerous. Among them, the following can be mentioned:

-   -   phases that comprise only lime C and alumina A, such that:        -   the phase of monocalcium aluminate CaAl₂O₄ noted as CA, of            which the crystalline lattice comprises one molecule of lime            C for one molecule of alumina A,        -   the phase of monocalcium dialuminate CaAl₄O₇ noted as CA2,            of which the crystalline lattice comprises one molecule of            lime C for two molecules of alumina A,        -   the phase of monocalcium hexa-aluminate noted as CA6, of            which the crystalline lattice comprises one molecule of lime            C for six molecules of alumina A,        -   the phase of tricalcium aluminate noted as C3A, of which the            crystalline lattice comprises three molecules of lime C for            one molecule of alumina A,        -   the phase of dodecacalcium hepta-aluminate noted as C12A7,            of which the crystalline lattice comprises two molecules of            lime C for seven molecules of alumina A;    -   phases that comprise only lime C and silica S, such that:        -   the phase of monocalcium silicate noted as CS, of which the            crystalline lattice comprises one molecule of lime C for one            molecule of silica S;        -   the phase of dicalcium silicate noted as C2S, of which the            crystalline lattice comprises two molecules of lime C for            one molecule of silica S,        -   the phase of tricalcium silicate noted as C3S, of which the            crystalline lattice comprises three molecules of lime C for            one molecule of silica S;        -   the phase of tricalcium bisilicate noted as C3S2, of which            the crystalline lattice comprises three molecules of lime C            for two molecules of silica S;    -   phases that comprise only alumina A and silica S, such that:        -   the phase of tri-aluminate bisilicate noted as A3S2, of            which the crystalline lattice comprises three molecules of            alumina A for two molecules of silica S;    -   phases comprising lime C, alumina A and silica S, such that:        -   the phase of dicalcium alumina silicate noted as C2AS, of            which the crystalline lattice comprises two molecules of            lime C for one molecule of alumina A and one molecule of            silica S,        -   the phase of monocalcium alumina bisilicate noted as CAS2,            of which the crystalline lattice comprises one molecule of            lime C for one molecule of alumina A and two molecules of            silica S;

this list being not a complete list.

These mineralogical phases are generally chosen according to theproperties that they provide the calcium aluminate cement with, inparticular in terms of reactivity and of mechanical property of thehardened final material.

It is common to graphically represent in a ternary diagram the variousmineralogical phases that a calcium aluminate can adopt according to therelative proportion of each one of the three compounds lime C, alumina Aand silica S in said calcium aluminate.

Such a ternary diagram is shown in FIG. 1 which shows some of thedifferent mineralogical phases that can coexist in a calcium aluminate,according to the mass proportion of lime C, of alumina A and of silica Scontained in said calcium aluminate.

In this diagram, it is possible to read the mass fraction of lime Ccontained in the calcium aluminate on the side of the triangle locatedbetween the vertices A and C, the mass fraction designating the weightof the lime C contained in the calcium aluminate with respect to thetotal weight of lime C, of alumina A and of silica S contained in saidcalcium aluminate.

This mass fraction of lime C is located inside the ternary diagram allalong a line parallel to the side of the triangle opposite the vertex C.

Similarly, it is possible to read the mass fraction of alumina Acontained in the calcium aluminate on the side of the triangle locatedbetween the vertices S and A, and this mass fraction of alumina A islocated inside the ternary diagram all along the line parallel to theside of the triangle opposite the vertex A.

Likewise, the mass fraction of silica S contained in the calciumaluminate on the side of the triangle located between the vertices C andS, and this mass fraction of silica S is located inside the ternarydiagram all along the line parallel to the side of the triangle oppositethe vertex S.

Furthermore, in the ternary diagram, particular points appear thatrepresent pure mineralogical phases. In other words, if the compositionof the crystalline portion of the calcium aluminate corresponds exactlyto the molar fraction of lime C, of alumina A and of silica S of thisparticular point, then said crystalline portion of the calcium aluminatecomprises 100% of this particular crystallised mineralogical phase. Thisis the case for example on point C2AS, or point CA or points CA2 or CA6.

In practice, it is rare for the calcium aluminate to comprise a singlepure phase, it more generally comprises several phases that coexist.Here, in the calcium aluminate according to the invention, the majoritycrystallised mineralogical phases are as follows:

-   -   the phase CA2, referred to as first crystallised mineralogical        phase,    -   the phase C2AS, referred to as second crystallised mineralogical        phase.

More particularly, remarkably, the mass fraction of all of said firstand second mineralogical phases CA2, C2AS in said calcium aluminate isgreater than or equal to 80%.

In other words, the cumulative weight of the first and secondmineralogical phases CA2, C2AS represents at least 80% of the totalweight of the calcium aluminate of the cement of calcium aluminatesaccording to the invention.

As such, contrary to the calcium aluminates described in prior art, ofwhich the majority mineralogical phase is the phase CA, here, themajority mineralogical phase or phases are the first and secondmineralogical phases CA2, C2AS.

The remaining 20% of the calcium aluminate of the cement according tothe invention, by weight with respect to the total weight of saidcalcium aluminate, can include minority mineralogical phases such as:

-   -   the phase CA, referred to as third crystallised mineralogical        phase, and    -   the phase CA6, referred to as fourth crystallised mineralogical        phase.

Indeed, as shown in the ternary diagram of FIGS. 1 and 2, these thirdand fourth mineralogical phases CA, CA6 are located in the immediatevicinity of the first and second mineralogical phases CA2, C2AS, in sucha way that, during the manufacture of the calcium aluminate of thecement according to the invention, it is very likely to form these thirdand fourth mineralogical phases CA, CA6.

Preferably, the mass fraction of all of the third and fourthcrystallised mineralogical phases CA, CA6 in said calcium aluminate ofthe calcium aluminate cement according to the invention is less than orequal to 20%.

The remaining 20% of the calcium aluminate of the cement according tothe invention can also include the minority compounds that constitutethe impurities of the calcium aluminate according to the inventionmentioned hereinabove: iron oxide Fe₂O₃ (F), titanium oxide TiO₂ (T),sulphur oxide SO₃ ($), magnesium oxide MgO, or alkaline compounds.

In particular, the minority compounds can form mineralogical phases withat least one of the majority compounds of the calcium aluminate whichare alumina A, lime C and silica S.

In particular, the remaining 20% of the calcium aluminate of the calciumaluminate cement according to the invention can include an additionalmineralogical phase of sulfocalcium aluminate C4A3$ comprising fourcalcium oxides CaO for three aluminium oxides Al₂O₃ and one sulphuroxide SO₃.

This additional mineralogical phase C4A3$ having a crystalline latticecomprising four molecules of lime C for three molecules of alumina A andone molecule of sulphur oxide $ is also called Ye'elimite.

The calcium aluminate cement according to the invention can thus include0.5% to 15%, preferably from 0.5% to 12%, of this additionalmineralogical phase of sulfocalcium aluminate C4A3$, by weight withrespect to the total weight of said calcium aluminate.

Advantageously, the minority phase Ye'elimite has an effect on thereactivity of the cementitious composition. In particular, the more theproportion of the minority phase Ye'elimite C4A3$ increases in thecementitious composition, the more the viscosity, at ambienttemperature, of this cementitious composition increases. This effect iseven more pronounced when the temperature around the cementitiouscomposition increases.

The minority phase Ye'elimite also has an effect on the reactivity ofthe cementitious composition at high temperature. In particular the morethe proportion of the minority phase Ye'elimite C4A3$ increases in thecementitious composition, the more the setting time is extended at hightemperature.

In the framework of the manufacture of a cement suited for anapplication in oil well drilling, choosing a composition of calciumaluminate that comprises a non-zero proportion of the minority phaseYe'elimite seems particularly advantageous. In particular, a proportionbetween 3 and 5%, for example equal to 3%, 4% or 5% of the phaseYe'elimite C4A3$ is appropriate.

This remaining 20% also includes the amorphous portion of the calciumaluminate of the cement according to the invention, if one exists.

In the ternary diagram of FIGS. 1 and 2, there is a particular straightline D that connects the particular points that represent the first andsecond mineralogical phases CA2, C2AS.

If the calcium aluminate of the cement according to the inventionbelongs to this particular straight line D, then it comprises between100% of first mineralogical phase CA2 and 100% of second mineralogicalphase C2AS.

In other words, if the calcium aluminate of the cement according to theinvention belongs to this particular straight line D, this calciumaluminate is crystalline, and the mass fraction of all of said first andsecond mineralogical phases CA2, C2AS in the calcium aluminate of thecement according to the invention is equal to 100%.

Thus, in order for the mass fraction of all of said first and secondmineralogical phases CA2, C2AS in said calcium aluminate to be greaterthan or equal to 80%, this calcium aluminate must be located in a zone Zclose to this particular straight line D.

This zone Z is shown graphically in the FIGS. 1 and 2. The points v, w,x and y of the figures correspond to the following mineralogicalcompositions:

-   -   the point v comprises 80% of first mineralogical phase CA2 and        20% of fourth mineralogical phase CA6,    -   the point w comprises 80% of first mineralogical phase CA2 and        20% of third mineralogical phase CA,    -   the point x comprises 80% of second mineralogical phase C2AS and        20% of third mineralogical phase CA, and    -   the point y comprises 80% of first mineralogical phase C2AS and        20% of fourth mineralogical phase CA6.

Thus, the surface of the ternary diagram delimited by the contour thatconnects the points [v—CA2—w—x—C2AS—y—v] corresponds to the zone Zinside of which the sum of the first and second phases CA2, C2AS isgreater than or equal to 80%.

Furthermore, it is possible to retrieve the chemical composition of acalcium aluminate by knowing its position in the ternary diagram.

For example, the composition of the point Y of the ternary diagram ofFIGS. 1 and 2 is 34.4% in lime C, 48.1% in alumina A, and 17.5% insilica S.

Thus, according to the same principle, the ranges of the chemicalcomposition in line C, in alumina A and in silica S of any calciumaluminate that belong to the zone Z can also be determined graphicallyon the ternary diagram using FIG. 2.

Of course, when minority compounds are present in the calcium aluminate,it is still possible to position this calcium aluminate in the ternarydiagram by determining the relative proportions of lime C, of alumina Aand of silica S in relation to the total weight of lime C, alumina A andsilica S comprised in this calcium aluminate.

Moreover, surprisingly, the first and second mineralogical phases CA2,C2AS have a particular reactivity when they are in the presence ofwater.

Indeed, these first and second mineralogical phases CA2, C2AS react verylittle with water at ambient temperature. In other terms, they areadapted to react very slowly with water at ambient temperature.

It is understood here that a mineralogical phase reacts with water whenit is hydrated by the water, and it is possible to characterise thisreactivity with a magnitude called “degree of hydration” of themineralogical phase.

The degree of hydration translates the capacity of a mineralogical phaseto be hydrated by water, i.e. that the molecules that constitute thecrystalline lattice of said mineralogical phase pass into solution inthe water in the form of ions, in other words the degree of hydrationassesses the ability of the bonds that exist between the molecules thatconstitute the mineralogical phase to be broken by the interaction withwater.

Nevertheless, as shall be demonstrated in the examples, the first andsecond mineralogical phases CA2, C2AS are adapted to react efficientlywith water under the effect of an increase in temperature.

In other words, the degree of hydration of these first and secondmineralogical phases increases with the temperature.

In particular, these first and second mineralogical phases CA2, C2AS areable to react with water much more quickly when the cure temperature isbetween 50 degrees Celsius (° C.) and 300° C., preferably between 80° C.and 280° C. than at ambient temperature.

Advantageously, it is furthermore possible to adjust the relativequantity of each one of first and second mineralogical phases CA2, C2AScomprised in the calcium aluminate cement according to the invention inorder to adjust the reactivity of the calcium aluminate cement accordingto the invention at this temperature, starting from the degree ofhydration of the first and second crystallised mineralogical phases CA2,C2AS at a given temperature.

Contrary to the first and second mineralogical phases CA2, C2AS, thethird mineralogical phase CA is known to be very reactive at ambienttemperature when it is in the presence of water, that is why its massfraction in the calcium aluminate of the cement according to theinvention is maintained less than or equal to 20% in such a way as tomaintain the characteristics of long workability of the cement accordingto the invention.

The fourth mineralogical phase CA6 is entirely inert regardless of thetemperature to which it is subjected, ambient or high. As such, it isnot hydrated even during an increase in temperature.

On the other hand, when it is present in the calcium aluminate, itcontributes substantially to the high cost of production of said calciumaluminate as it contains a lot of alumina which is the most expensiveportion of said calcium aluminate. That is why its mass fraction in thecalcium aluminate of the cement according to the invention is maintainedless than or equal to 20%.

Thus, very advantageously, as the cement according to the inventioncomprises little of these third and fourth phases CA, CA6, it reactsslowly when it is mixed with water at ambient temperature, withoutneeding to add a retarder, and it is advantageous from an economic pointof view.

For example, a calcium aluminate cement according to the invention thatis particularly interesting, comprises, by weight with respect to thetotal weight of said calcium aluminate:

-   -   50% to 60% of first crystallised mineralogical phase CA2;    -   26% to 32% of second crystallised mineralogical phase C2AS;    -   2.5% to 3.5% of third crystallised mineralogical phase CA;    -   0.5% to 1.5% of a fifth crystallised mineralogical phase of        tetracalcium ferro-aluminate C4AF;    -   10% to 15% of additional crystallised mineralogical phases.

As such, this composition according to the invention has both a majorityof first and second crystallised mineralogical phases CA2, C2AS and aminority of crystallised mineralogical phases CA, CA6.

More precisely, an example of calcium aluminate cement according to theinvention that can be considered comprises exactly, by weight withrespect to the total weight of said calcium aluminate:

-   -   55% of first crystallised mineralogical phase CA2;    -   29% of second crystallised mineralogical phase C2AS;    -   3% of third crystallised mineralogical phase CA;    -   1% of a fifth crystallised mineralogical phase of tetracalcium        ferro-aluminate C4AF;    -   12% of additional crystallised mineralogical phases.

The additional crystallised mineralogical phases include in particularfor example the phase Ye'elimite C4A3$. This example of calciumaluminate cement according to the invention comprises for example, byweight with respect to the total weight of said calcium aluminatebetween 0.5% and 12% of this phase Ye'elimite C4A3$.

More precisely, in the example given hereinabove, the calcium aluminatecement comprises for example 4% of this phase Ye'elimite, comprised inthe 12% of additional crystallised mineralogical phases.

In the diagram of FIG. 2, this particular composition is found at pointI. It is very close to the particular straight line D and even appearsto belong to this particular straight line D in FIG. 2.

Moreover, in order to manufacture the calcium aluminate cement accordingto the invention, an operator co-grinds, i.e. mixes and grinds in asingle operation, bauxite and limestone until a powder is obtained thatcomprises particles of which the maximum diameter is less than or equalto 100 micrometres (μm).

The co-grinding operation can be carried out using a ball mill or anyother mill known to those skilled in the art.

The powder obtained at the end of this co-grinding operation is thengranulated with water, i.e. the fine particles of powder areagglomerated thanks to the water in order to form granules of a diameterexceeding that of the powder.

These granules are then introduced into a crucible made of alumina whichis itself introduced into an electric oven. The electric oven containingthe crucible is brought to a temperature of 1400° C. according to atemperature gradient of 600° C. per hour. When the oven has reached1400° C., a cooking stage of 6 hours is applied.

At the output of the electric oven, the granules of calcium aluminateare ground finely in order to form the powder that forms the calciumaluminate cement according to the invention.

Advantageously, the calcium aluminate cement powder according to theinvention has a Blaine specific surface area measured according tostandard NF-EN-196-6, between 2200 square centimetres per gram and 4500square centimetres per gram.

Preferably, the Blaine specific surface area of the calcium aluminatecement according to the invention is between 2900 and 3900 squarecentimetres per gram.

The higher the Blaine specific surface area is, the finer the grainsconstituting the powder are.

Furthermore, advantageously, the cement according to the inventionhaving such a Blaine specific surface area is adapted during its mixingwith water, to have an optimal contact surface with this water.

Furthermore, the cement according to the invention having this Blainespecific surface area is adapted to be mixed homogeneously with a largequantity of water, i.e. the cement is adapted to be dispersed in a largequantity of water equivalently at all points of the mixture.

In other words, even in the presence of a substantial quantity of water,the cement according to the invention does not bleed.

The calcium aluminate cement according to the invention can be mixedwith water in order to form a cementitious composition.

More precisely, the cementitious composition according to the inventioncan include compounds other than the calcium aluminate cement accordingto the invention, such as:

-   -   cementitious additions chosen from: fly ash and/or a granulated        blast furnace slag and/or a silica flour and/or silica fume        and/or metakaolin,    -   granulates with more or less large diameters chosen from: quartz        and/or fine limestone and/or sand, and    -   adjuvants of any kind known to those skilled in the art, for        example thinning agents or setting retarders.

These lists of other compounds possibly contained in the cementitiouscomposition are not limiting.

Fly ash corresponds to the ashes obtained during the combustion at highpressures and temperatures of the pulverised coal.

Very fine fly ash referred to as pulverised fly ash or fly ash withlarger dimensions referred to as furnace bottom ash can in particular beadded. The commercial products EN4750 “N” fly ash® from the companyScotash, or class F bottom ash® from the company FlyAshDirect areexamples of these.

Table 1 hereinbelow gives the main physical-chemical characteristics ofthese fly ashes.

TABLE 1 Fly Ash EN450“N” fly ash Class F bottom ash Company ScotashFlyAshDirect Blaine Specific 3110 2000 Surface Area (cm²/g) d50 (μm)14.0 23.1 Density 2.27 2.49 LOI 1000° C. (%) 4.8 na

Here, the LOI (Loss on Ignition) groups together volatile elements.

The granulated blast furnace slag come from the surface layer that isformed during the fusion of the iron in blast furnaces, said surfacelayer being separated from the iron in fusion and then cooled in theform of granules in order to form said slag.

The commercial product Slag® from the company Ecocem is an example ofthis.

Table 2 hereinbelow gives the main physical-chemical characteristics ofthis slag.

TABLE 2 Slag Slag Company Ecocem Blaine Specific 4500 Surface Area(cm²/g) d50 (μm) 12.7 Density 2.93

The silica fume is a pozzolanic material comprising amorphous silica. Itis generally a secondary product from the production of alloys ofsilicon and/or of ferrosilicon in electric arc furnaces. It can havedifferent aspects: it can it particular be found in the form of veryfine powder, or hard granules of a few millimetres in diameter.

The commercial products 971U® from the company Elkem and Dray Powder S®from the company Norchem are examples of this.

Table 3 hereinbelow gives the main physico-chemical characteristics ofthese silica fumes.

TABLE 3 Silica fume 971U Dry Powder S Company Elkem Norchem BlaineSpecific 16400 1640 Surface Area (cm²/g) d50 (μm) 10.3 ~560 Density 2.242.29

The metakaolin is an anhydrous and slightly crystalline aluminiumsilicate produced by dehydroxylation of the kaolin at high temperatures.

The commercial product Metasial V800® from the company Soka (KaolinièreArmoricaine Company) is an example of this.

Table 4 hereinbelow gives the main physico-chemical characteristics ofthis metakaolin.

TABLE 4 Metakaolin Metasial V800 Company Soka Blaine specific 14100surface area (cm²/g) d50 (μm) 4.0 Density 2.75

In practice, the cementitious composition can for example include:

-   -   from 0% to 50% of cementitious additions, by weight with respect        to the dry weight of the cementitious composition, and/or    -   from 50% to 100% of calcium aluminate cement according to the        invention, by weight with respect to the dry weight of the        cementitious composition;

the dry weight of the cementitious composition corresponding to thetotal weight of all of the compounds comprised in said cementitiouscomposition except water.

Thus, the cementitious composition can for example include 0%, 5%, 10%,15%, 20%, 25%, 30%, 35%, 40%, 45% or 50% of cementitious additions, byweight with respect to the dry weight of the cementitious composition,and/or 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% ofcalcium aluminate cement according to the invention, by weight withrespect to the dry weight of the cementitious composition.

Regardless of the compounds comprised in the cementitious composition,the calcium aluminate cement present reacts with the water, i.e. achemical reaction is produced, commonly called “hydration”, between thecalcium aluminate cement and the water, during which the moleculesconstituting the crystalline and/or amorphous portions of the cementaccording to the invention are hydrated by the water, namely they passinto solution in the water in the form of ions.

Conventionally, due to this chemical reaction, the consistency of thecementitious composition formed by the mixture between the water and thecement according to the invention is able to change over time.

More precisely, three phases of change in said cementitious compositioncan be detected, with these three phases constituting the “globalhardening” of the cementitious composition:

-   -   a first phase, referred to as thickening phase, during which the        viscosity of the cementitious composition increases slowly,        without preventing the implementation thereof;    -   a second phase, referred to as setting phase or hydraulic        setting phase, during which the cementitious composition hardens        quickly; and,    -   a third phase, referred to as the final hardening phase, during        which the cementitious composition continues to harden more        slowly.

The duration of the thickening phase can vary from one cement to anotherin that it greatly depends on the reactivity of the cement used.

The open time globally corresponds to the duration of this thickeningphase. It is about a few hours in general.

In practice, the duration of the thickening phase can vary from a fewminutes to a few hours according to the application considered, thecement and the adjuvants that are possibly added.

In the case of an application in oil wells, the thickening phasegenerally lasts a few hours.

The duration of the thickening phase also depends on external parameterssuch as the pressure, temperature, and the relative proportion betweenthe water and the cement.

During the hydraulic setting phase, the cementitious composition passesrapidly from a liquid state to a solid state, with these states beingdefined in the mechanical sense of the term, namely that the liquidstate is a state wherein the cementitious composition is irreversiblydeformed when it is subjected to a deformation, while the solid state isa state wherein the cementitious composition can be deformed elasticallywhen it is subjected to a deformation.

In practice, it is considered that the cementitious composition hasreached its solid state when, subjected to the Vicat test according tothe ASTM C91 standard described hereinafter in the example part, theVicat needle is unable to fully pass through the cementitiouscomposition. On the contrary, it is considered that the cementitiouscomposition is in its liquid state when, subjected to this same Vicattest, the Vicat needle passes fully through the cementitiouscomposition.

As such, at the end of the hydraulic setting phase, the cementitiouscomposition already has a hardened aspect, in such a way that it can beconsidered as a hardened final material. However, it continues to hardenduring the final hardening phase.

In practice, here, the invention proposes a use of the calcium aluminatecement according to the invention, according to which

a) a cementitious composition is realised by mixing said calciumaluminate cement with water,

b) said cementitious composition is put in place,

c) said cementitious composition is heated to a temperature between 50°C. and 300° C., preferably between 80° C. and 280° C., in such a way asto favour the setting of the cementitious composition.

In step a), a user forms the cementitious composition by mixing thecalcium aluminate cement with all of the said other compounds possiblycomprised in the cementitious composition, and with water.

Initially, i.e. at the time when the water, the cement and possibly saidother compounds are mixed, the consistency of the cementitiouscomposition formed is more or less fluid according to the weight of thewater that it contains in relation to the total weight of saidcementitious composition.

The quantity of water added to the cement according to the invention andto said possible other compounds mainly depends on the application forwhich the cementitious composition is intended.

For example, a user can choose to form a cementitious composition in theform of a rather non-fluid paste.

According to a particular use of the calcium aluminate cement accordingto the invention, in step a), the user can form an aqueous suspension ofcement.

More precisely, in the case where the cementitious composition is anaqueous suspension exclusively formed by water and the cement accordingto the invention, the mass fraction of the water in said aqueoussuspension is between 15% and 45%.

The mass fraction of the water in this aqueous suspension, comprisedbetween 15% and 45%, amounts to a water/cement ratio comprised between20% and 70%, said ratio being the ratio between the weight of the waterand the weight of the dry cement forming the aqueous suspension.

In the case where the cementitious composition is an aqueous suspensionand comprises water, the calcium aluminate cement according to theinvention and cementitious additions, the mass fraction of the water insaid aqueous suspension is between 20% and 60%, for example equal to29%, 31%, 33%, 37%, 52%, or 55%.

The mass fraction of the water in this aqueous suspension, comprisedbetween 20% and 60%, amounts to a water/dry compound ratio between 25%and 150%, said ratio being the ratio between the weight of the water andthe dry weight of the cementitious composition that comprises the cementand the cementitious additions. For example, the water/dry compoundratio of the aqueous suspension is equal to 41%, 48%, 60%, 80%, 110%, or120%.

These general considerations are known to those skilled in the art andthe proportion of water to be added to the cement and to the possibleother compounds in order to obtain a cementitious composition of whichthe consistency is adapted to each type of application shall not bediscussed hereinafter in any further detail.

In step b), as long as the cementitious composition is in the thickeningphase, the user can set the cementitious composition in place.

For example, if the cementitious composition has the form of an aqueoussuspension, the user can pour the cementitious composition into a slot.

In particular, according to the particular use of the calcium aluminatecement according to the invention in the form of an aqueous suspension,in step b), said aqueous suspension is injected into an oil drillingwell.

This injection is carried out by means of one or several pumps that pushthe aqueous suspension into a tubular body to the bottom of the drillingwell. Once it arrives at the bottom of this drilling well, thissuspension can naturally move back up to the surface, between the rockwall and the tubular body.

When the cementitious composition is in the form of a paste, the usercan shape it in such a way as to pre-fabricate objects of the beam orslab type.

In step c), the triggering of the hydraulic setting phase of thecementitious composition is favoured by a heating of the cementitiouscomposition to a temperature between 50° C. and 300° C., preferablybetween 80° C. and 280° C.

More precisely, this heating of the cementitious composition can bevoluntary or be endured.

Thus, in practice, according to the particular use of the cementitiouscomposition in the form of an aqueous suspension for oil drilling wells,this aqueous suspension of cement is naturally heated between 50° C. and300° C. by the surrounding rock, after moving back up to the surface.

For example, at a depth located between 3000m and 5000m under thesurface, the temperature is generally between 120° C. and 180° C., andthe heating of the cementitious composition is then endured.

Thus, advantageously, according to the particular use of the calciumaluminate cement according to the invention, the aqueous suspension hasa satisfactory workability at ambient temperature, i.e. its viscosity atambient temperature is sufficiently low to allow it to be injected bymeans of pumps, and the hardening of said aqueous suspension is producedafter it is injected into the wells, when the surrounding temperaturerises.

Advantageously, there is no need to add a retarder to the aqueoussuspension formed as such.

The user can also choose to activate the phenomenon of the hydraulicsetting of the cementitious composition according to the invention byheating said cementitious composition to a temperature chosen between50° C. and 300° C. This is therefore a voluntary heating.

Advantageously, the user can thus choose the moment when the hydraulicsetting phase is triggered, by choosing the moment when he heats thecementitious composition.

Whether the heating is voluntary or is endured, the thickening phase,which globally corresponds to the open time, is complete at the momentof this heating.

EXAMPLES

In the part that follows, examples have been implemented in order toassess the properties of the calcium aluminate cement according to theinvention, and to compare them with those of other existing cements.

To do so, various cementitious compositions have been formed fromvarious calcium aluminate cements, of which the cement according to theinvention, and these cementitious compositions have been characterisedusing several tests.

Two main aspects make it possible to characterise a cementitiouscomposition: its workability which translates the open time during whichthe cementitious composition has a viscosity adapted to its use, and itshardening kinetics.

The hardening kinetics reflect the speed of thickening of thecementitious composition and the instant from which the hydraulicsetting is initiated, as well as the mechanical resistance reached bythe hardened final material obtained from the cementitious compositionafter the latter has reacted with the available added water, at the timedesired according to the application.

The characteristics of workability and of hardening kinetics can bequantified in different ways, by different test methods and according todifferent standards. Thus, these characteristics of workability and ofhardening kinetics can be quantified by different characteristic timesmeasured, for example a gelling time, a time for initial setting or athickening time, such as defined hereinafter.

Of course, according to the uses planned for the cementitiouscompositions, the workability and the hardening kinetics sought canvary.

I. Preliminary Tests

1/Cements Compared

In practice, here, a first, a second, and a third calcium aluminatecement (Cement1, Cement2, Cement3) were used in order to form differentcementitious compositions of which the properties were compared.

More precisely, the first and second cements (Cement1, Cement2) arecalcium aluminate cements of prior art known under the commercialdenominations of Ciment fondu® and SECAR®71.

The third cement (Cement3) is a calcium aluminate cement according tothe invention.

It is obtained according to the industrial method described hereinabove,by co-grinding 63.5% of Bauxite and 36.5% of Limestone, by weight withrespect to the total weight of the co-ground materials.

Table “Composition” hereinbelow shows the chemical composition measuredfor this third cement Cement3 according to the invention, as well as thechemical composition of the raw materials used in order to obtain it(Bauxite and Limestone). These compositions are given as a percentage byweight (%), i.e. they indicate the weight of the compound with respectto the total dry weight of the cement or of the raw material used.

TABLE “Composition” Cement3 Bauxite Limestone SiO2 (%) 7.02 7.67 0.30Al2O3 (%) 58.90 77.59 0.20 Fe2O3 (%) 2.85 2.30 0.08 CaO (%) 26.62 3.6955.52 MgO (%) 0.52 0.39 0.28 SO3 (%) 0.20 0.16 0.03 K2O (%) 0.55 0.910.02 Na2O (%) 0.07 0.16 0.00 TiO2 (%) 2.78 3.72 0.00 P2O5 (%) 0.17 0.150.00 Mn2O3 (%) 0.01 0.02 0.00 Cr2O3 (%) 0.03 0.08 0.00 LOI (%) 0.28 2.7843.54

The LOI line (Loss on Ignition) here groups together the volatileelements such as the residual humidity in the case with bauxite orcarbon dioxide CO2 in the case with limestone.

Table 5 hereinbelow gives the mineralogical phases contained in thesefirst, second and third cements (Cement1, Cement2, Cement3). Themineralogical phases were measured by a known technique of X-raydiffraction (often shortened to DRX).

TABLE 5 CA CA2 C2AS C2S Ferrites Other Cement1 55% na  3% 9% 11% 22%Cement2 60% 40% na na na na Cement3  3% 55% 29% na  1% 12%

The notation na means that the cement does not compnse the correspondingmineralogical phase or that these phases are present in very lowunmeasured quantities.

The mineralogical phase Ferrites substantially comprises themineralogical phase of tetra-calcium ferro-aluminate C4AF, called inwhat follows sixth crystallised mineralogical phase. The crystallisedlattice of this sixth crystallised mineralogical phase comprises fourmolecules of lime C for one molecule of alumina A and one iron oxideFe₂O₃, shortened to the letter F.

The “Other” column groups together the impurities comprised in thesecements, namely at least one of the following compounds: iron oxideFe₂O₃, titanium oxide TiO₂, sulphur oxide SO₃, magnesium oxide MgO, andalkaline compounds.

In particular, the “Other” column of the cement Cementl of prior artcomprises the mineralogical phases CA6 and C4A3$. More precisely, thecement Cementl comprises 0% of phase CA6 and about 0.7% of C4A3$, byweight with respect to the total weight of all of the phases containedin said Cementl.

The cement Cement3 comprises 3% of phase CA6 and 4% of phase C4A3$, byweight with respect to the total weight of all of the mineralogicalphases contained in said Cement3.

In light of the industrial manufacturing of this third calcium aluminatecement according to the invention, the proportion of the mineralogicalphases that it comprises can vary slightly from one manufacturingcampaign to another.

Thus, another cement according to the invention Cement3bis having theproportions of mineralogical phases described in Table 6 was alsoobtained in conditions similar to the conditions of obtaining the thirdcement according to the invention Cement3.

TABLE 6 CA2 (%)* 59.2 C2AS (%)* 22.5 CT ortho. (%) 4.6 CA6 (%) 5.4 CA(%) 0.9 Spinel MA (%) 1.2 C4A3$ (%) 4.2 C4AF (%) 0.6 Fer spinel (%) 0.7Alu α (%) 0.5 C12A7 (%) 0.0 MgO (%) 0.2 CaO (%) 0.2

This other calcium aluminate cement according to the invention, thuscomprises 72.5% of mineralogical phase CA2 and 27.5% of mineralogicalphase C2AS, by weight with respect to the two mineralogical phases CA2,C2AS only.

A reference cement (CementRef) was also used in comparing the first,second and third calcium aluminate cements Cement1, Cement2, Cement3.

This reference cement CementRef is a Portland cement of class G that isconventionally known to those skilled in the art and often used inapplications of the oil drilling type.

The reference cement CementRef has a Blaine specific surface area ofabout 3010 cm²/g.

2/Thickening Time

A first test that made it possible to characterise the studied cementsconsisted in measuring the thickening time of different cementitiouscompositions obtained by mixing these cements with water.

The thickening time is a piece of information that makes it possible toassess the workability of the cementitious composition, in particularwhen it has the form of an aqueous suspension.

In the meaning that is intended here, the thickening time is anestimation of the duration at the end of which the cementitiouscomposition can no longer be pumped. In other words, this is theduration at the end of which an aqueous suspension is too viscous to beable to be displaced by means of a pump.

More precisely, the thickening time corresponds to the duration that haselapsed between the moment when the water and the cement have been mixedin order to form the cementitious composition in the form of aqueoussuspension, and the moment when the consistency, referred to as Beardenconsistency (Bc), of the cementitious composition has reached a valuesuch that this cementitious composition can no longer be pumped, whereinthe Bearden consistency is expressed using a magnitude without a unit.

Here, the measurement of the thickening time is achieved according tothe standard “ISO 10426-1, clause 10.3”, from document “Petroleum andnatural gas industries—Cement and materials for well cementing”, ofwhich the first part NF-EN-ISO-10426-1 is entitled “Part1—Specifications” and is based on the standard ISO 10426-1:2005, and thethickening time is such that the cementitious composition has reached aBearden consistency of 100 Bc, at 23° C., under an atmospheric pressureof 1 atmosphere (atm).

In practice, the measuring of this thickening time is carried out forexample by means of a brewing blade adapted to rotate in thecementitious composition while measuring a torque. This measured torquemakes it possible to assess the force that the blade has to exert on thecementitious composition in order to be able to rotate. This torque isthus related to the Bearden consistency of the cementitious composition.

Table 7 hereinbelow shows different cementitious compositions that wereformed using the three calcium aluminate cements Cement1, Cement2,Cement3, and Portland cement CimentRef, as well as the thickening timethat is associated to them, at ambient temperature (23° C.).

In practice, these cementitious compositions were formed at 23° C., bymixing the cement with the appropriate quantity of water (indicated intable 7) for 15 seconds under stirring at 4000 revolutions per minute(rpm). An additional stirring at 12,000 revolutions per minute for 35seconds was then carried out.

In this table 7, the water/cement ratio represents the weight of thewater that was introduced in order to form the cementitious composition,with respect to the weight of the dry cement.

TABLE 7 Name of the cementitious Water/cement Thickening timecomposition Cement used ratio (hours:minutes) Compo1 Cement1 0.5% 1:21Compo2 Cement2 0.5% 0:48 Compo3 Cement3 0.38 10:26  CompoRef CimentRef0.44 5:38

In table 7, it can be seen that the cementitious compositions Compo1 andCompo2 formed using the calcium aluminate cements of prior art Cement1and Cement2 have relatively short thickening times (less than 2 hours)at ambient temperature (23° C.). If a user needs more time than thesethickening times in order to be able to use the cementitiouscompositions comprising the two cements Cement1 and Cement2, he willhave to add setting retarders to them.

The cementitious composition CompoRef comprising the CimentRef confirmsthat Portland cements have an average thickening time (around 5 hours)at ambient temperature (23° C.). That is why these cements are oftenused in applications that require a rather long implementation time.

The cementitious composition Compo3 comprising the calcium aluminatecement according to the invention Cement3 has a thickening time greaterthan 10 hours, which offers the possibility to the user to use—forexample to transport, pour, inject, pump, etc.—this cementitiouscomposition Compo3 for a long time, and this without having to addretarder therein.

Furthermore, it has a thickening time nearly twice as long as that ofthe cementitious composition CompoRef at ambient temperature (23° C.),even though it comprises less water and should therefore be morereactive than the cementitious composition CompoRef.

The cement according to the invention Cement3 therefore has very highworkability without adding setting retarder. Thus, it is particularlysuitable for applications that require a very long open time, and thiswithout chemical pollution linked to the use of setting retarders.

3/Viscosity

A second test that made it possible to characterise the cements studiedconsisted in measuring the viscosity of certain cementitiouscompositions.

3a. Fann®35 Viscometer

The viscosity makes it possible to assess the hardening kinetics and theworkability of these cementitious compositions.

This is here about measuring the rheology of the cementitiouscompositions, i.e. their ability to flow and/or to be deformed.

In the meaning that is intended here, measuring the viscosity is carriedout according to the standard ISO 10426-2, clause 12. This standardcomes from the second part of the “Petroleum and natural gasindustries—Cement and materials for well cementing”, said part entitled“Part 2—Testing of well cements” and based on the publication API RP10B, 22nd edition, of December 1997, addendum 1, of October 1999.

More precisely, the implementing of the viscosity test is carried out asfollows: the cement is mixed with the chosen quantity of water in orderto form the cementitious composition (operating method detailedhereinabove), then this cementitious composition is placed in a rotatingviscometer of the brand FANN®, model 35.

The rotating viscometer FANN®35 is said to be “with direct indication”.In practice, two coaxial cylinders are plunged vertically into thecementitious composition. The outer cylinder—also called a sleeve—isdriven in rotation by a motor at a speed chosen by the operator. Theinner sleeve is linked to the frame by a torsion spring. Thecementitious composition, set into movement by the outer cylinder,exerts a torque on the inner sleeve, and this torque is proportional tothe angle of torsion of said spring.

The direct reading of the angle of torsion of the spring (in degrees) islinked to the shear stress (in Pascal) of the cementitious composition,which translates the viscosity of said cementitious composition. Thismeasurement is commonly referred to as “FANN®35 reading”.

In practice, the outer cylinder rotates at a rotation speed chosen bythe operator with a potentiometer, ranging from 3 to 300 revolutions perminute, and a crosshair makes it possible to visually measure on agraduated disc the angle of rotation of the spring linked to the innersleeve, wherein this angle of torsion is proportional to the torquegenerated by the cementitious composition in movement on the innersleeve.

It is then possible to follow the change of the angle of torsion of thespring linked to the inner sleeve, according to the rotation speed ofthe outer cylinder.

It is furthermore possible to test on a one-off basis the cementitiouscomposition in order to estimate its viscosity directly after the mixingbetween the cement and the water (Initial viscosity V1), or after a restperiod of 10 minutes (Viscosity V2), at a temperature of 23° C., of 50°C. or of 80° C. and at atmospheric pressure of about 1 atmosphere (atm),for a rotation speed of the viscometer of 3 revolutions per minute(rpm).

In practice, as indicated hereinabove, the values read are those of theangle of torsion of the spring linked to the inner sleeve of theviscometer Fann®35.

Table 8 hereinbelow shows the various cementitious compositions testedand gives the values of the angle of torsion of the inner sleeverepresentative of their respective viscosity V1 and V2 at 23° C., table9 shows similar cementitious compositions and values of the angle oftorsion of the inner sleeve that are representative of their viscosityat 50° C., and table 10 shows the same cementitious compositions asthose of table 9 and values of the angle of torsion of the inner sleevethat are representative of their viscosities at 80° C.

In these three tables 8, 9 and 10, the cementitious compositions testeddepend on the cement used and the Blaine specific surface area chosenfor the cement as well as the water/cement ratio chosen.

The values indicated for the viscosities V1 and V2 are here the valuesof the angle of torsion measured.

TABLE 8 Blaine Water/ Specific Initial Cementitious Cement cementSurface Area viscosity Viscosity composition used ratio (cm² · g⁻¹) V1V2 Compo5 Cement2 0.41 4000 14 >300 Compo6 Cement3 0.41 2200 6 21 Compo7Cement3 0.41 3080 10 37 Compo8 Cement3 0.41 3470 13 38 Compo9 Cement30.41 3700 14 36 Compo10 Cement3 0.41 4100 18 58

Thus, the cementitious composition Compo5 comprising the calciumaluminate cement of prior art Cement2 has an initial viscosity V1 thatis acceptable in order to be able to be manipulated, i.e. for a settingup for example by pumping, but its viscosity after 10 minutes is that ofa gelled cementitious composition. Consequently, as soon as thecementitious composition Compo5 is left immobile for an excessive periodof time, it can no longer be manipulated. This is particularlycompromising when it is desired to displace such a cementitiouscomposition using pumps, which would then risk being damaged whenstarting up after temporary stoppage.

In contrast, the cementitious compositions Compo6 to Compol0 accordingto the invention are particularly advantageous in that their initialviscosities V1 are low (less than 20), which facilitates their transportby means of a pump. Their viscosity V2 after a time of rest also remainssufficiently low so that they can be pumped.

Thus, the hardening kinetics of the cementitious compositions comprisingthe calcium aluminate cement Cement3 according to the invention is muchslower, at ambient temperature, than those of the cementitiouscompositions of prior art, which is an advantage for uses that require along manipulation.

Furthermore, table 8 also gives an indication of the reactivity of thecalcium aluminate cement Cement3 according to the invention according tothe Blaine specific surface area. One indeed notes that the more theBlaine specific surface area increases, the more the initial viscosityand the viscosity after rest increase. Thus, the hardening kineticsaccelerates when the Blaine specific surface area increases, whichtranslates the fact that the finest grains of powder are more easilyhydrated by water as they have a larger reactive surface.

TABLE 9 Blaine Water/ Specific Initial Cementitious Cement cementSurface Area viscosity Viscosity composition used ratio (cm² · g⁻¹) V1V2 Compo11 Cement2 0.48 4000 24 >300 Compo12 Cement3 0.48 3470 13 67Compo13 Cement3 0.48 4100 20 121 Compo14 Cement3 0.48 4400 27 145

By comparing tables 8 and 9, it is observed that the initial viscosityof the cementitious composition Compo11 of table 9 comprising thecalcium aluminate cement Cement2 of prior art increases when thetemperature increases, even though it comprises more water than thesimilar cementitious composition Compo5 of table 8.

Furthermore, as in the case of the cementitious composition Compo5, theviscosity V2 after a pause of the cementitious composition Compo11 isalso excessively substantial for this cementitious composition Compol 1to be able to be used in pumps without adding setting retarder to it.

Moreover, the cementitious compositions according to the inventionCompol2 to Compo14 have low initial viscosities V1 and viscosities V2after a pause time that still allows for their use as well as theirtransport by means of pumps.

Furthermore, at this temperature (50° C.), the Blaine specific surfacearea plays an important role on the viscosity: the more the Blainespecific surface area increases, the more the viscosity increases.

TABLE 10 Cementitious composition Initial viscosity V1 Viscosity V2Compo11 >300 >300 Compo12 7 138 Compo13 14 195 Compo14 28 270

Table 10 shows that at 80° C., the cementitious composition Compo11comprising the calcium aluminate cement of prior art Cement2 cannot beused because its viscosity is too high as soon as it is mixed withwater.

The initial viscosity V1 of the cementitious compositions comprising thecement Cement3 according to the invention is of the same order ofmagnitude at 80° C. as at 50° C.

However, the increase in temperature influences the viscosity V2 after apause time of the cementitious compositions Compo12 to Compo14. Indeed,the viscosity after a pause clearly increases between 50° C. and 80° C.,and all the more so if the Blaine specific surface area is large. Thisconfirms the fact that the temperature favours the reaction between thewater and the cement Cement3 according to the invention.

3b. Anton Paar Viscometer

Moreover, other measurements of viscosity can be taken with an AntonPaar viscometer (or rheometer).

In practice, the Anton Paar rheometer is referenced as MCR_302C). It isprovided with a with a cup CC27 and with a mixing baffle with 6 straightrectangular blades of 16 millimetres (mm) high over 9 mm long, around ashaft of 4 mm in diameter.

The Anton Paar viscometer makes it possible to follow the change of theviscosity as a function of time, at a given temperature, when the bladeis rotating at a chosen speed.

To do this, the rheometer measures in reality the torque applied by thecementitious composition on the blade in rotation in said cementitiouscomposition.

The torque measured is representative of the viscosity of thecementitious composition.

Here, the change in this torque as a function of time has been followed,at 80° C., when the blade imposes a shear rate of 500 s⁻¹.

Thanks to the curve obtained, it is possible to go back to the beginningof the setting, namely to the so-called “gel” (or gelling) timecorresponding to the location of the change in the slope of the curvethat represents the torque as a function of time.

Following table 11 shows in parallel the viscosity measured by theFann®35 viscometer after 10 minutes of rest (V2), and the gelling timeof the two cementitious compositions according to the inventioncomprising the cement Cement3bis, and of the cementitious composition ofprior art comprising the Portland cement CementRef.

TABLE 11 Blaine Specific Gelling time Cementitious Water/Cement SurfaceArea Viscosity V2 (minutes) Composition Cement used Ratio (cm² · g⁻¹)(Fann ®35, 23° C.) (Anton Paar, 80° C.) Compo15 Cement3bis 0.41 3070 3848 Compo16 Cement3bis 0.48 3070 25 77 CompoRef CementRef 0.44 3010 30 90

Moreover, the experimental results show that the cementitiouscompositions comprising the cement Cement3bis according to the inventionare less viscous in short times than that comprising the Portlandreference cement.

Furthermore, the cementitious compositions compol5 and compol6 accordingto the invention show a clean and fast setting compared to thecomposition CompoRef. The rupture in the slope of the experimental curvebetween the thickening phase and the setting phase is then highlymarked.

Finally, on can note that the gelling time depends on the water/cementratio applied to the cement according to the invention.

4/Measurement of Bleeding

Measuring bleeding consists in determining the mass of water thatappears on the surface of a given quantity of aqueous suspension, afterimmobilisation of this aqueous suspension for 2 hours.

The water that appears on the surface is given as a percentage (%), byweight with respect to the total weight of the water added to theaqueous suspension.

In order for the aqueous suspension to be accepted from the standpointof the standards of the “American Petroleum Institute (API)”, themaximum percentage authorised of water bled is 5.9%.

In practice, measuring bleeding is here carried out at 23° C., in acylindrical container with a capacity of 250 millilitres (ml).

Following table 12 gives the percentages of water bled of the threecompositions Compo15, Compo16 and CompoRef studied hereinabove.

TABLE 12 Blaine Specific Water Cementitious Cement Water/Cement SurfaceArea bled Composition used Ratio (cm² · g⁻¹) (%) Compo15 Cement3bis 0.413070 1.0 Compo16 Cement3bis 0.48 3070 2.8 CompoRef CementRef 0.44 30104.8

Note here that the cement according to the invention bleeds less thanthe reference cement, even at higher water/cement ratios, which isfavourable for ensuring its conformity with the API standards.

5/Mechanical Resistance

On the other hand, it is also possible to assess the hardening kineticsof the cementitious compositions by measuring the mechanical resistancereached by the hardened final material obtained after reaction betweenthe water and the cement.

In practice, the cementitious composition is formed by mixing the waterand the cement, then the cementitious composition is allowed to rest for24 hours, at a chosen temperature and at a chosen pressure, beforemeasuring the mechanical resistance according to the standard ISO10426-1, clause 9.2.

Table 13 shows the mechanical resistances of the three cementitiouscompositions Compo1, Compo2 and Compo3 after 24 hours at 37° C. andunder atmospheric pressure (R1), after 24 hours at 60° C. and underatmospheric pressure (R2), and after 24 hours at 110° C. and underpressure of 20.7 MegaPascal (R3).

The mechanical resistances R1, R2 and R3 are given in MegaPascal (MPa).

TABLE 13 Mechanical Mechanical Mechanical Cementitious resistance R1resistance R2 resistance R3 composition (MPa) (MPa) (MPa) Compo1 6.3 6.411.8 Compo2 17.4 21.5 25.2 Compo3 0 0.8 23.6

From 37° C., the mechanical resistance developed by the cementitiouscompositions Compo1 and Compo2 comprising calcium aluminate cementsCement1 and Cement2 according to prior art is substantial, whichconfirms the fact that these cementitious compositions Compo1 and Compo2react at low temperature.

On the contrary, the cementitious composition Compo3 comprising thecement Cement3 according to the invention has a zero mechanicalresistance at 37° C., and a practically zero one at 60° C., whichindicates that this cement reacts only very little under 60° C. Thus,this supports the fact that the reaction of the cement according to theinvention with water is naturally retarded at temperatures less than 60°C., without having to add a retarder.

After 24 hours at 110° C., the mechanical resistances of thecementitious compositions Compo1 and Compo2 are higher, which provesthat these cementitious compositions react more quickly at thistemperature than at a temperature of 37° C.

At 110° C., the cementitious composition Compo3 also develops amechanical resistance of about twenty megaPascals. Thus, the reactionbetween the cement according to the invention and the water is favouredby high temperatures.

Consequently, the calcium aluminate cement according to the inventionhas a hardening kinetics that is naturally controlled by thetemperature, without needing to add a retarder.

Furthermore, at 110° C., the mechanical resistance R3 developed by thecementitious composition Compo3 comprising the calcium aluminate cementCement3 according to the invention is similar to that of the calciumaluminate cements that are usually used and known to date (of about 20MPa).

It is therefore adapted to similar applications.

6/Setting Time and Contamination

6a. Test with Vicat Needle

Another test dealt with the effect of the contamination of a cementPortland by a cement according to the invention.

To this effect, a measurement was taken of the setting time of thevarious cementitious compositions that comprise both a Portland cementand a calcium aluminate cement.

In the meaning that is intended here, the setting time is measuredaccording to the standard ASTM C91, using a Vicat needle.

The Vicat test consists in mixing water with the cement in order to formthe cementitious composition, then in allowing a Vicat needle to fallinto the cementitious composition, which is static, at regular intervalsof time. As long as the needle sinks to the bottom of the cementitiouscomposition, it is considered that the setting time has not beenreached, as soon as it sinks without being able to go to the bottom ofthe cementitious composition, the setting time has been reached.

In practice, the setting time therefore corresponds to the duration thathas elapsed between the moment when the cement and the water were mixedin order to form the cementitious composition in a liquid state, and themoment when the cementitious composition passed to a state that issufficiently solid so that the Vicat needle cannot pass entirely throughit but only partially, at a temperature of 23° C. and under atmosphericpressure (1 atm).

Table 14 hereinbelow shows the setting times, in minutes, of differentcementitious compositions comprising a certain proportion of calciumaluminate cement mixed with a Portland cement. The Portland cement usedis a Portland cement of class H.

In this table 14, the percentages give the weight of the calciumaluminate cement added with respect to the total dry weight of thecement used. Thus, the complement for reaching 100% corresponds to theweight of Portland cement contained in the total dry weight of thecement.

The water/cement ratio is 0.38, i.e. the weight of the water usedrepresents 38% of the total dry weight of the cement used.

TABLE 14 Calcium aluminate cement used 0% 5% 8% 15% Cement1 400 310 22020 Cement2 400 190 45 10 Cement3 400 340 320 300

Table 14 shows the effect on the setting time of the contamination of aPortland cement by a calcium aluminate cement.

According to table 14, the calcium aluminate cements of prior artCement1 and Cement2 have a substantial effect on the setting time of thePortland cement used. Indeed, while the Portland cement alone,corresponding to the first column, has a relatively long setting timethat is of 400 minutes, the setting time observed for a mixture with 15%of calcium aluminate cement Cementl and Cement2 is very short (20 and 10minutes respectively). This means that a cementitious compositioncontaining a Portland cement and a calcium aluminate cement of prior artreacts ultra quickly, preventing the use of such a cementitiouscomposition for applications that require long implementations. Suchcementitious compositions therefore cannot be used in applications ofthe drilling well type for example.

In contrast, the contamination of the Portland cement by the cementCement3 according to the invention has only very little effect, atambient temperature, on the setting time of the cementitiouscomposition. Indeed, the setting time of a cementitious compositioncomprising 15% of Cement3 and 85% of Portland cement corresponds to 75%of the setting time of a cementitious composition comprising 100% ofPortland cement.

Consequently, the use of the calcium aluminate cement Cement3 accordingto the invention is facilitated as compared to the other calciumaluminate cements in that it is not necessary to perfectly clean theinstallations before being able to use these installations for aPortland cement.

6b. Test Via Anton Paar Rheometer

Moreover, other tests have made it possible to measure the effect of thecontamination of a Portland cement by a cement according to theinvention, or of the contamination of a cement according to theinvention by a Portland cement.

These tests consisted in following the torque exerted by thecementitious compositions on the blade of the Anton Paar rheometerrotating at a constant shearing speed of 500 s⁻¹, as a function of time,at 20° C. or at 80° C.

The curve obtained makes it possible to deduce the gelling time (such asis explained in the point 3b. Anton Paar Viscometer hereinabove).

The curve obtained also makes it possible to determine the durationelapsing between the formation of the cementitious composition and themoment when the torque reaches 4 mN.m.

This duration makes it possible to quantify the “setting time” of thecementitious composition. This is a value of this setting time that isnot necessarily equal to the value of the setting time measured by theVicat test.

For this measurement, the cementitious compositions are prepared asfollows: 100 g of cement are mixed with 44 g of water (i.e. awater/cement ratio of 0.44), using a Rayneri Turbotest mixer, for 15seconds at 1000 revolutions per minute, then for 120 seconds at 3300revolutions per minute.

Table 15 hereinbelow shows the results obtained.

TABLE 15 Cements used Time measured at 20° C. CimentRef Cement3bisCement2 20° C. (%) (%) (%) gelling (min) setting (min) 0 100 0 420 42010 90 0 420 420 25 75 0 190 260 90 10 0 420 420 90 0 10 10 10 100 0 0420 420

In this table 15, the percentages are given by weight with respect tothe total weight of the cement.

When the value of the gelling time and/or of the setting time is 420minutes, this means that the experiment was stopped before the materialhas undergone gelling or setting. In these cases, the gelling andsetting times are in reality much higher than 420 minutes.

Note that when the Portland cement CimentRef is contaminated with up to10% of cement Cement3bis according to the invention, at 20° C., thegelling and setting times are not affected, i.e. they are similar tothose obtained for the Portland cement CimentRef alone.

In contrast, when the Portland cement is polluted with 10% of the cementof prior art Cement2 at 20° C., the setting and gelling times falldramatically: they are both of 10 minutes.

Moreover, when the cement Cement3bis according to the invention ispolluted with up to 10% of Portland Cement CementRef at 20° C., thegelling and setting times are not affected, i.e. they are similar tothose obtained for the cement Cement3bis alone.

When the cement according to the invention Cement3bis is polluted with25% of Portland cement CementRef, the gelling and setting times remainsatisfactory: they are respectively about 190 minutes and 260 minutes.

As such, the use of the calcium aluminate cement according to theinvention is facilitated at ambient temperature with respect to cementsof prior art in that it is not necessary to clean the installationsafter or before using these installations with Portland cement.

7/Degree of Hydration

A last test consisted in assessing the influence of the temperature onthe degree of hydration of the cement Cement3 according to theinvention.

This test is based on observations under the scanning electronmicroscope allowing for an elementary chemical analysis as well as onmeasurements of X-ray diffractions that allow for a quantification ofthe mineralogical phases according to the Rietveld method.

In practice, a cementitious composition Compo15 was formed by mixingwater with the cement Cement3 according to the invention in awater/cement ratio of 0.44, i.e. in such a way that the water represents44% by weight with respect to the total dry weight of the cement.

A cementitious composition Compo16 was also formed by mixing water withthe cement Cement2 of prior art in a water/cement ratio of 0.44.

These cementitious compositions Compo15 and Compo16 were then subjectedto an X-ray diffraction test as soon as they were formed (D1), after acure, i.e. a rest at 23° C. for 24 hours (D2), after a passage in theautoclave for 24 hours at 120° C. (D3), and after a passage in theautoclave for 24 hours at 180° C. (D4).

The results of this X-ray diffraction test make it possible to estimatethe percentage of each mineralogical phase present in the cementitiouscompositions Compo15 and Compo16 as well as the remaining free water, byweight with respect to the total weight of the cementitious compositionCompo15, according to the treatment that they were subjected to.

The results also make it possible to estimate the percentage of hydratesformed during the hydration reaction of the water with the cementsCement3 and Cement2, according to the different treatments that areundergone. Hydrates are compounds formed between the water (noted as H)and the hydrated chemical compounds coming from the mineralogical phasescomprised initially in the cements studied.

In other words, the results of the X-ray diffraction test make itpossible to estimate the degree of hydration of the mineralogical phasesof the cement according to the invention Cement3 or of the cement ofprior art Cement2, according to the temperature.

“Free water” means the water that is not engaged in the bonds with ionscoming from the various hydrated mineralogical phases, i.e. which doesnot already belong to a formed hydrate. In other words, this is thewater that is still available to react with (or hydrate) the anhydrousmineralogical phases that still exist.

In tables 16 and 17, the “other” phase groups together the possibleimpurities (iron oxide Fe₂O₃, titanium oxide TiO₂, sulphur oxide SO₃,magnesium oxide MgO, and alkaline compounds).

Table 16 hereinbelow shows the results of the X-ray diffraction test,namely the percentage of each mineralogical phase and of each hydratepresent after each treatment undergone by the cementitious compositionCompo15.

Table 17 shows the results of the X-ray diffraction test, after eachtreatment undergone by the cementitious composition Compo16.

TABLE 16 Phases D1 D2 D3 D4 CA2 39%  36%   0% 0% C2AS 20%  20%  14% 11% Other 10%  8%  8% 8% Free water 31%  26%  16% 19%  CAH10 0% 6%  0% 0%C3AH6 Katoite 0% 0% 27% 22%  C3AS(3-x)H4x 0% 0%  0% 7% Hibshite AH3Gibbsite 0% 4% 14% 0% AH Boehmite 0% 0% 21% 33% 

In table 16, the “other” phase also comprises the phase CA. This phaseCA is present initially during the mixture between the cement3 and water(column D1), and is absent from the mixture after 24 hours of reaction(columns D2, D3 and D4) as it has fully reacted with the water,regardless of the temperature.

The “Other” line further comprises the phase CA6. Here, the phase CA6represents 2.3%, by weight, of all of the phases comprised in thecomposition Compo15 at the time of the diffraction D1, 2.6% by weight,of all of the phases comprised in this composition at the time of thediffraction D2, 2.2% by weight, of all of the phases comprised in thiscomposition at the moment of the diffraction D3 and 2% by weight of allof the phases comprised in this composition at the moment of thediffraction D4.

As shown in table 16, the first and second mineralogical phases CA2,C2AS react little, even not at all, under 120° C.

However, the first mineralogical phase CA2 reacts fully from 120° C. Inother words, starting at 120° C., the first mineralogical phase CA2 isentirely hydrated by the water.

The second mineralogical phase C2AS reacts starting at 120° C., but itis less reactive than the first mineralogical phase CA2.

Thus, the reactivity of the first mineralogical phase CA2 is favoured bya temperature less than that favouring the reactivity of the secondmineralogical phase C2AS.

The CA6 does not react regardless of the temperature, the variations inthe composition being attributed to the uncertainties inherent to themeasuring method.

TABLE 17 Phases D1 D3 D4 CA 40%  0% 0% CA2 27%  0% 0% Other 2% 0% 0%Free water 31%  2% 11%  C3AH6 Katoite 0% 45%  44%  AH3 Gibbsite 0% 41% 0% AH Boehmite 0% 12%  45% 

By comparing tables 16 and 17, note that the hydrates C3AH6, AH3, and AHformed by the hydration reaction of the calcium aluminate cement ofprior art Cement2 with water are also formed by the hydration reactionof the calcium aluminate cement according to the invention Cement3 withwater.

Furthermore, during the hydration reaction of the calcium aluminatecement Cement3 according to the invention with water, an additionalhydrate C3AS_((3-x))H_(4x) is also formed.

Thus, the presence of the same hydrates in the hardened final materialobtained from the calcium aluminate cement Cement2 of prior art and inthe hardened final material obtained from the calcium aluminate cementCement3 according to the invention shows that the properties of chemicalresistance of these hardened final materials are similar.

Consequently, the cement according to the invention has properties ofchemical resistance similar to those of the calcium aluminate cementsalready known.

Thus, all the experiments conducted show that the calcium aluminatecement according to the invention has a slow hardening kinetics atambient temperature, which makes it possible to use it without settingretarder.

This hardening kinetics can be adjusted according to the temperature andby choosing the relative proportion of first and of second mineralogicalphase CA2, C2AS.

Furthermore, at ambient temperature, the calcium aluminate cementaccording to the invention has a low contaminating power on Portlandcements.

Finally, the mechanical properties of the hardened final materialobtained from the calcium aluminate cement according to the inventionare similar to those of the hardened final materials obtained usingknown calcium aluminate cements.

8/Density of the Cementitious Composition

In the case of oil drilling applications, the density determines thecapacity of the cementitious composition used in the oil wells to retainthe gases and the oil contained in said wells.

The density is assessed by relating the weight of the aqueous suspensionto its volume.

In practice, here is measured the weight of 250 ml of aqueoussuspension.

The density is expressed in “pounds per gallon (ppg)”, knowing that 1ppg is 0.12 kilogram per cubic decimetre (kg/dm³) or 0.12 gram per cubiccentimetre (g/cm³).

Following table 18 presents the specific density of the cementitiouscompositions comprising the Cement3bis according to the invention andthe Portland cement CementRef.

TABLE 18 Blaine Specific Cementitious Water/cement Surface Area Densitycomposition Cement used ratio (cm²/g) (ppg) Compo15 Cement3bis 0.41 307016.0 Compo16 Cement3bis 0.48 3070 15.3 CompoRef CimentRef 0.44 3010 15.8

Thus, one can note that the densities of the cementitious compositionsCompo15 and Compo16 according to the invention are similar to that ofthe Portland reference cement and therefore adapted to the applicationsfor oil drilling.

II. Additional Tests

1/Cements Compared

A fourth, a fifth and a sixth calcium aluminate cement according to theinvention (Cement4, Cement5, Cement6) were used in order to formdifferent cementitious compositions of which the properties werecompared.

The fourth, fifth and sixth cements Cement4, Cement5, Cement6 areobtained in the laboratory using the following practically pure rawmaterials: the source of silica Millisil E400®, the source of aluminaAL170® and the source of limestone Calcite Normapu®. The exactcompositions of these raw materials are given in the table 19hereinbelow.

In practice, the cements Cement4, Cement5 and Cement6 are obtainedaccording to the following operating mode:

-   -   Weighing of raw materials;    -   Co-grinding of the raw materials in the jar-rotator, in a tank        of 6 litres, of the brand Linatex, for about 16 h, until a        powder is obtained comprising particles of which the maximum        diameter is less than or equal to 100 micrometres (μm);    -   Granulating with water according to a technique known to those        skilled in the art referred to as “disc granulating” in order to        obtain granules from about 1 cm to 3 cm in diameter;    -   Steaming of these granules at 110° C., for at least 15 h;    -   cooking in a crucible made of alumina introduced into an        electric oven;    -   grinding;    -   Fin grinding in the steel ball mill BB10® model in order to        obtain a Blaine specific surface area close to 3000 cm²/g.

In order to reach the desired cooking temperature, the temperaturegradient applied is 600° C. per hour.

Following table 19 summarises the operating conditions and the weightsof the raw materials mixed in order to form the cements Cement4, Cement5and Cement6.

TABLE 19 Cement4 Cement5 Cement6 Alumina 720.0 g 500.0 g 662.0 g Al170Silica E400  35.0 g 150.0 g  63.0 g Limestone 429.8 g 614.0 g 480.7 gNormapur Cooking 12 h 1550° C. 16 h 1525° C. 16 h 1525° C. (Duration inhours and temperature in degrees Celsius) Number of 7500 9000 8000revolutions during fin grinding

Table 20 hereinafter gives the chemical composition of the raw materialsused to obtain the laboratory cements Cement4, Cement5, Cement6, as wellas the composition of the cements Cement4, Cement5 and Cement6effectively obtained.

TABLE 20 Source Source Source of silica of of lime- Millisil aluminastone Ce- Ce- Ce- E400 Al170 CaCO₃ ment4 ment5 ment6 PaF (%) 0.29 0.6343.93  na na na SiO₂ (%) 98.51  na 0.06 3.4 15.1 6.2 Al₂O₃ (%) na 99.17 0.1  72.3  50.6 66.5  Fe₂O₃ (%) 0.06 0.03 0.14 1.1  0.2 0.7 CaO (%) 0.020.02 55.32  24.3  34.9 27.2  MgO (%) na 0.01 na na na na SO₃ (%) 0.080.07 0.05 0.1  0.1 0.1 K₂O (%) na na na na na na Na₂O (%) 0.08 0.05 na0.1  0.1 0   TiO₂ (%) 0.03 0.02 0.02 na na na P₂O₅ (%) 0.01 0.01 na nana na Mn₂O₃ (%) 0.01 0.01 0.01 na na na Cr₂O₃ (%) 0.02 0.01 0.02 na nana

Table 21 hereinbelow gives the mineralogical phases contained in thefourth, fifth and sixth cements (Cement4, Cement5, Cement6).

TABLE 21 Cement4 Cement5 Cement6 CA (%) 0 0.1 0.4 CA6 0 0 0.4 CA2 (%)84.8 32.6 70 C2AS (%) 15 66.9 28.8 C2S (%) 0 0 0 Ferrites (%) 0 0 0C4A3$ 0 0 0 Alumina (%) 0 0.3 0.1 Lime (%) 0.1 0.2 0.1 Quartz (%) 0.1 00.2 Other (%) 0 0 0

The “alumina” and “lime” lines represent the remainder of the rawmaterials that did not form mineralogical phases.

The cements Cement4, Cement6 and Cement5 are respectively shown in thediagram in FIG. 2 at points J, K and L of the straight line D.

Following table 22 gives the Blaine specific surface area, the densityand the diameter d50 (μm) of the cements Cement4, Cement5, Cement6obtained.

In practice, the density here corresponds to the density of the cementcompared to the density of the pure water. The density is measured witha pycnometer.

The diameter d50 corresponds to the median diameter d50 of any set ofparticles. This is a representative magnitude of the statisticdistribution of the sizes of these particles, in other words of thegranulometry of this set of particles.

The median diameter d50 is a reference diameter defined as the diameterunder which is 50% of the particles studied, in volume in relation tothe total volume of all of said particles studied.

In other words, for a set of particles having a given median diameterd50, 50% by volume of these particles has a diameter less than thisgiven median diameter d50, and 50% by weight of these particles have adiameter greater than this given median diameter d50.

“Diameter” here means the largest dimension of the particle, regardlessof its shape.

TABLE 22 Blaine Specific Surface Area (cm²/g) d50(μm) Density Cement43110 33 2.94 Cement5 3690 16 3.00 Cement6 3070 25 2.95

Cementitious compositions were formed using cements according to theinvention Cement4, Cement5 and Cement6.

These cementitious compositions were formed at 23° C., by mixing 346grams of cement with 142 grams of water (i.e. a water/cement ratio of0.41) for 15 seconds under stirring at 4000 revolutions per minute, thenfor 35 seconds under stirring at 12,000 revolutions per minute.2/Rheological Tests

The rheological tests were conducted using an Anton Paar viscometer.

As hereinabove, the Anton Paar rheometer used is referenced as MCR_302®.It is provided with a cup CC27 and with a mixing baffle comprising 6straight rectangular blades 16 millimetres (mm) high over 9 mm longabout a shaft 4 mm in diameter.

The change, as a function of time, of the torque generated by thevarious cementitious compositions on the blade of the viscometerexerting a shear speed of 500 s⁻¹, at 80° C. was plotted.

The three cementitious compositions each one comprising the cementsCement4, Cement5 and Cement6 have relatively short gelling times: 7minutes for the compositions comprising the cements Cement4 and Cement6,and 9 minutes for the composition comprising the cement Cement5. Thechange, as a function of time of the torque generated by thecementitious composition comprising the cement Cement4 according to theinvention on the blade of the viscometer exerting a shear speed of500s⁻¹, was plotted at 80° C. and at 23° C.

At 23° C., the composition undergoes a gelling about 30 minutes afterthe mixing between the water and the cement Cement4. However, at thistemperature, the composition is not subjected to any setting phase inthe 8 hours of the experiment.

On the contrary, at 80° C., the setting is relatively fast: the gellingtime observed is about 7 minutes followed by a setting phase.

Thus, the reactivity of the composition comprising the cement Cement4according to the invention is increased by temperature, since thegelling time is shorter and the setting is faster.

3/Bleeding

The bleeding experiment described hereinabove was conducted again on thecementitious compositions comprising the cements Cement4, Cement5, andCement6 according to the invention.

Following table 23 shows the results of this experiment.

Blaine Specific Water Cementitious Cement Water/cement Surface Area bledcomposition used ratio (cm²/g) (%) Compo17 Cement4 0.41 3110 0 Compo18Cement5 0.41 3690 0.4 Compo19 Cement6 0.41 3070 0.2

One can note that the percentages of bled water are very low andentirely satisfactory to meet the API standards.

4/Density of the Cementitious Compositions

As explained in point 1.8, the density of the cementitious compositionsCompo17 to Compo19 was measured. The corresponding results are shown inthe following table 24.

TABLE 24 Blaine Specific Cementitious Cement Water/cement Surface AreaDensity composition used ratio (cm²/g) (ppg) Compo17 Cement4 0.41 311016.6 Compo18 Cement5 0.41 3690 16.4 Compo19 Cement6 0.41 3070 16.1

Thus, one can note that the densities of the cementitious compositionsCompo17 to Compo19 according to the invention are similar to that of thePortland reference cement and therefore suited for applications in oildrilling.

5/Hydration and Mechanical Resistance

5a. Ultrasound Test According to Atandard API RP 10B-2

This is a non-destructive test that consists in measuring thepropagation time of ultrasounds through a sample of cementitiousmaterial, here through the initial slurry, of known dimension, in theprocess of setting and hardening.

Generally, the more the material hardens, the shorter the time requiredfor the ultrasound to pass through this material is.

Thus, the structuring steps of the material subjected to differentchosen conditions of temperature and of pressure can be followed.

This propagation time is then compared to the propagation times obtainedwith standard test specimens of which the mechanical resistance isevaluated via conventional breakage tests.

It is then possible to deduce the value of the mechanical resistance ofthe material, referred to as “mechanical resistance by ultrasound”, bycomparing it with the measurements taken on standard test specimens.

In order to implement this test, it is suitable in a first step tomanufacture the cementitious compositions.

In practice, the manufacture of the cementitious compositions is similarto that indicated in part 1.2 of the examples, which corresponds to amanufacture according to the standard API RP 10B-2 Clause 5.

The compositions obtained are those given in tables 23 and 24hereinabove.

The measurement of the propagation times of the ultrasounds through thesample is carried out according to the standard API RP 10B-2 Clause 8,i.e. water and the cement are mixed, the cementitious composition isintroduced into the measuring cell where it is placed under atemperature gradient ranging from 26.6° C. to 121° C. in 4 hours, thenunder a constant temperature of 121° C. for 20 hours, and where apressure of 3000 psi is applied as soon as it is introduced into themeasuring cell. The mechanical resistance by ultrasound is assessedduring the change of the material du to increase in temperature andpressure.

Here, the mechanical resistances of the various cementitiouscompositions Compo15 and Compo17 to Compo19 are measured 12 hours afterthe beginning of the thermal treatment, i.e. after the 4 hours oftemperature gradient and the first 8 hours of the temperature stage, and24 hours after the beginning of the thermal treatment, i.e. at the endof the thermal treatment comprising the 4 hours of temperature gradientsand the 20 hours of the temperature stage.

The mechanical resistances of the cementitious compositions are asfollows

-   -   after 12 hours of treatment: 34 MegaPascals (MPa) for the        Compo17, 1.5 MPa for the Compo18, 17 MPa for the Compo19, and 16        MPa for the Compo15;    -   after 24 hours of treatment: 34 MPa for the Compo17, 3 MPa for        the Compo18, 19 MPa for the Compo19 and 21 MPa for the Compo15.

As these results show, the composition Compo19 comprising the Cement6manufactured in the laboratory has a mechanical resistance by ultrasoundthat is comparable to that of the composition Compo15 comprising theCement3bis manufactured industrially, as these cements have anequivalent content in phase CA2 and C2AS.

Moreover, it can be noted that the mechanical resistance by ultrasoundof the composition Compo14 comprising the Cement4 is clearly greaterthan the mechanical resistance of the composition Compo19 comprising theCement6, which itself is clearly greater than the mechanical resistanceof the composition Compo18 comprising the Cement5.

Consequently, it can be deduced that the mechanical resistance byultrasound increases with the mass ratio CA2/C2AS of the cements used.

However, the mechanical resistance of the composition Compo18 comprisingthe Cement5 is still very low, the hydration of the correspondingcomposition probably not being sufficiently advanced at the time of themeasurement (24 hours).

5b. Autoclave Test

The cementitious compositions are carried out according to the sameprotocol as for the tests in the Anton Paar viscometer.

The cementitious compositions were introduced into a mould comprisingthree cylindrical cells (diameter 40 mm, height 50 mm), then placed inthe autoclave set to 180° C. with a pressure of 10 bars (145 PSI)generated by the vapour pressure.

After 24 hours of residence in the autoclave, the resistance tocompression of the cementitious compositions is measured by means of apress module. The compression speed is 2.4 kiloNewtons per second.

The composition Compo17 comprising the cement Cement4 has a mechanicalresistance to compression of 2113 PSI (14.6 MPa), that comprising thecement Cement5 (Compo18) of 561 PSI (3.9 MPa), and that comprising thecement Cement6 (Compo19) of 2330 PSI (16.0 MPa).

Then after a cure under a temperature of 120° C., such as undergoneduring the test carried out by using ultrasound described hereinabove,the composition Compo18 comprising the cement Cement5 according to theinvention developed a mechanical resistance by ultrasound equal to 10%of that of the composition Compo17 comprising the cement Cement4, themechanical resistance of this same composition Compo18 comprising theCement5 after a treatment at 180° C. in the autoclave is equal to 25% ofthat comprising the Cement4 (Compo17).

Thus, the higher the temperature is, the more the difference in themechanical resistance between the cementitious composition comprising acement according to the invention rich in C2AS and the cementitiouscomposition comprising a cement according to the invention rich in CA2tends to be reduced.

The cements according to the invention are intended for differentapplications for which a more or less great resistance is sought, at agiven time.

III Effects of the Minority Phase Ye'elimite C4A3$

1/Cements Compared

Moreover, three other cements Cement7, Cement8, Cement9 were alsomanufactured.

These are cements manufactured in the laboratory and intended toreproduce the cements obtained industrially by the method according tothe invention, when the raw materials used contain sulphur oxide SO₃, orwhen the sulphur oxide is introduced by the industrial method.

In practice, the cements Cement7, Cement8, Cement9 are obtained from thefollowing raw materials: limestone, bauxite A, bauxite B and anhydrouscalcium sulphate (shortened to C$), of which the respective chemicalcompositions are indicated in table 26 hereinafter.

In practice, 5 kg of each one of the cements Cement7, Cement8 andCement9 are obtained according to the following operating procedure:

-   -   Steaming of the raw materials at 110° C. for 24 hours in order        to dry them;    -   Co-grinding of the raw materials in a laboratory ball mill of        the “Blue Circle” type, at 1500 revolutions, followed by the        opening of the mill in order to clean the trap and an additional        grinding for an additional 400 revolutions.    -   Granulation of the raw materials with water according to a        technique known to those skilled in the art referred to as “disc        granulation” in order to obtain granules from about 5 mm to 20        mm in diameter;    -   Steaming of the granules at 110° C. for 24 hours in order to dry        them;    -   Cooking of the granules in three crucibles made of alumina, in        an oven of the brand Nabertherm® at 1375° C. for 12 hours (once        the temperature of 1.375° C. is reached) with a rise in the        temperature gradient of 10° C. per minute;    -   Cooling via inertia in the oven;    -   Grinding of the material obtained in order to form grains with a        diameter smaller than 3.15 mm;    -   Fin grinding of the grains obtained in the ball mill of the        “Blue Circle” type until a powder with a Blaine specific surface        area of about 3000 cm²/g is obtained.

Following table 25 summarises the operating conditions and the weightsof the raw materials mixed in order to form the cements Cement7, Cement8and Cement9.

TABLE 25 Cement7 Cement8 Cement9 Limestone (g) 34 34 33.4 Bauxite A (g)58.6 58.6 58.2 Bauxite B (g) 7 6 6 Anhydrite C$ (g) 0.4 1.4 2.4 CookingA stage of 12 hours at 1375° C., with a (Duration in temperaturegradient of 600° C. per hour. hours and temperature in degrees Celsius)

Table 26 hereinafter gives the chemical composition of the raw materialsused to obtain the cements Cement7, Cement8, Cement9 as well as that ofthe cements Cement7, Cement8, Cement9 obtained.

TABLE 26 Lime- Bauxite Bauxite Cement Cement Cement stone A B 7 8 9 SiO2(%) 0.13 7.66 0.93 6.5 4.9 4.9 Al2O3 (%) 0.29 68.86 77.80 64.3  66.0 64.0  Fe2O3 (%) 0.10 2.36 0.61 0.4 0.4 0.5 CaO (%) 56.21 0.54 0.02 25.9 25.7  26.0  MgO (%) 0.11 0.27 0.08 0.2 0.4 0.4 SO3 (%) 0.05 0.12 0.070.2 0.6 1.1 K2O (%) 0.00 0.87 0.05 na na na Na2O (%) 0.05 0.09 0.19 nana na TiO2 (%) 0.02 3.57 4.45 2.4 3.0 2.9 P2O5 (%) 0.01 0.21 0.17 na nana Mn2O3 (%) 0.01 0.03 0.01 na na na Cr2O3 (%) 0.01 0.03 0.02 na na naFeO na na na 0.1 0.1 0.1 H2O na na na 0   0   0   LOI (%) 43.02 15.3915.61 na na na

Table 27 hereinbelow gives the mineralogical phases contained in thecements Cement7, Cement8, Cement9. The mineralogical phases weremeasured using a known technique of X-ray diffraction (often shortenedto DRX).

TABLE 27 Cement7 Cement8 Cement9 CA2 54 60 54 C2AS 30 23 22 CA6 9 7 8 CTortho 4 5 5 C4A3$ 1 4 8 MA 1 1 1 CA 0 0 0 Ferrite 1 0 1

The phase MA corresponds to a phase comprising one molecule of magnesiumoxide MgO (noted as M according to cement-manufacturer notation) for onemolecule of alumina A.

Each one of the cements Cement7, Cement8, Cement9 comprises about 70% ofthe first mineralogical phase CA2 and 30% of the second mineralogicalphase C2AS, with respect to the total weight of these two mineralogicalphases.

Thus, they are equivalent, in terms of composition in these two phases,to the cements Cement3, Cement3bis and Cement6 according to theinvention.

As can be seen in table 27, the cements Cement7, Cement8 and Cement9include various proportions of the minority phase Ye'elimite C4A3$,namely respectively 1%, 4% and 8% of mineralogical phase C4A3$, byweight with respect to the total weight of the calcium aluminate cement,respectively Cement7, Cement8 and Cement9.

Thus, the proportions in mineralogical phases of the Cement8 make itsimilar to the calcium aluminate cements according to the inventionCement3 and Cement3bis.

Table 28 gives the Blaine specific surface area and the diameter d50(μm) of the cements Cement7, Cement8 and Cement9 obtained

TABLE 28 Blaine Specific Surface Area (cm²/g) d50(μm) Cement7 2950 34Cement8 3000 28 Cement9 3080 24

Cementitious compositions were formed using cements according to theinvention Cement7, Cement8 and Cement9.

These cementitious compositions were formed at 23° C., by mixing 346grams of cement with 152 grams of water (i.e. a water/cement ratio of0.44) for 15 seconds under stirring at 4000 revolutions per minute, thenfor 35 seconds under stirring at 12,000 revolutions per minute.

2/Rheological Tests

2a. Fann®35 Viscometer

As explained hereinabove in the part I. Preliminary tests, thanks to theFANN®35 viscometer, it is possible to follow the change of the torquegenerated by the cementitious composition on the inner sleeve, accordingto the rotation speed of the outer cylinder, and to test on a one-offbasis the cementitious composition in order to estimate its viscositydirectly after the mixing between the cement and the water (Initialviscosity V1), or after a rest period of 10 minutes (Viscosity V2), at atemperature of 23° C.

Table 29 shows the values of the angle of torsion of the retainingspring linked to the inner sleeve that are representative of theviscosity V1 and V2 of the cementitious compositions comprising thecements Cement7, Cement8, Cement9, as well as those of the cementitiouscompositions comprising the cement Cement3bis.

TABLE 29 Cemen- titious Water/ Blaine Phase compo- Cement cement SurfaceC4A3$ Viscos- Viscos- sition used ratio (cm²/g) (%) ity V1 ity V2Compo15 Cement3 0.41 3070 4 17 38 bis Compo16 Cement3 0.48 3070 4 9 25bis Compo20 Cement7 0.44 2950 1 13 32 Compo21 Cement8 0.44 3000 4 15 46Compo22 Cement9 0.44 3080 8 17 58

As such, as shown in table 29, the viscosities V1 and V2 of thecementitious compositions 20 to 22 comprising the cements Cement7,Cement8, Cement9 are satisfactory as they allow for the pumping of thesecementitious compositions at ambient temperature.

At 23° C., the viscosities V1 and V2 are slightly affected by thepercentage of the minority phase Ye'elimite C4A3$: the viscosities V1and V2 increase with the increase of the phase Ye'elimite.

The following table 30 gives the viscosity of the various cementitiouscompositions Compo16 and Compo20 to Compo22, at 23° C., when the outercylinder of the rheometer is rotating at 300 revolutions per minute (inthe process of increasing) then at 600 revolutions per minute.

TABLE 30 Viscosity Water/ Blaine Phase at 300 Cementitious Cement cementSurface C4A3$ revolutions composition used ratio (cm²/g) (%) per minuteCompo16 Cement3bis 0.48 3070 4 62 Compo20 Cement7 0.44 2950 1 75 Compo21Cement8 0.44 3000 4 100 Compo22 Cement9 0.44 3080 8 103

Again, it can be noted that at 23° C., the viscosity under high stressis slightly affected by the percentage of the minority phase Ye'elimiteC4A3$: the viscosity increases with the increase of the phaseYe'elimite.

2b. Anton Paar Viscometer

As explained hereinabove, the Anton Paar viscometer makes it possible tofollow the change of the viscosity as a function of time, at a giventemperature, when the blade is rotating at a chosen speed.

Here, the propeller rotates at 500s⁻¹, and the temperature is about 80°C.

Thanks to the curve obtained, it is possible to go back to the beginningof the setting, namely the so-called “gelling” time corresponding to thelocation of the change in the slope of the curve.

The change as a function of time of the torque generated by thecementitious compositions Compo20 to Compo22 on the blade of the AntonPar rheometer, at 80° C. was measured.

The effect of the minority phase Ye'elimite C4A3$ is substantial at 80°C., on the gelling time (which marks the beginning of the setting phase)as well as on the overall viscosity of the compositions.

Indeed, the gelling times are respectively about 30 minutes for thecomposition Compo20 comprising 1% of phase C4A3$, 5 hours and 20 minutesfor the composition Compo21 comprising 4% of phase C4A3$, and 6 hoursand 30 minutes for the composition Compo22 comprising 8% of phase C4A3$.

Thus, surprisingly, the more the quantity of the minority phaseYe'elimite increases in the cementitious composition, the greater theworkability is, i.e. the longer the open time is, or the longer thethickening phase is.

Consequently, it seems that the minority phase C4A3$ has a retardanteffect, at high temperature, on the setting of the cementitiouscompositions according to the invention.

Furthermore, the shearing stresses at 500 s⁻¹(linked to the dynamicviscosity) of the cementitious compositions during the thickening phaseare all the more large that the cementitious compositions include moreof the minority phase C4A3$: 150 Pa for the Compo20, around 250 Pa forthe Compo21, and around 500 Pa for the Compo22.

Thus, at 80° C., the dynamic viscosity of the cementitious compositionsfor the thickening phase seems to be highly affected by the increase ofthe minority phase Ye'elimite.

3/Bleeding

The bleeding experiment described hereinabove was conducted again on thecementitious compositions comprising the cements according to theinvention Cement7, Cement8, and Cement9.

Table 31 shows the results of this experiment.

TABLE 31 Blaine Specific Water Cementitious Cement Water/cement SurfaceArea bled composition used ratio (cm²/g) (%) Compo20 Cement7 0.44 29500.3 Compo21 Cement8 0.44 3000 1.1 Compo22 Cement9 0.44 3080 0.7

One can note that the percentages of water bled are very low andentirely satisfactory to meet the API standards.

4/Density

As explained in point 1.8, the density was measured of the cementitiouscompositions Compo20 to Compo22. The results are shown in followingtable 32.

TABLE 32 Blaine Specific Specific Cementitious Cement Water/cementSurface Area Density composition used ratio (cm²/g) (ppg) Compo20Cement7 0.44 2950 15.8 Compo21 Cement8 0.44 3000 15.5 Compo22 Cement90.44 3080 15.6

As such, note that the densities of the cementitious compositionsCompo20 to Compo22 according to the invention are suited for anapplication in oil drilling.

The presence of the minority phase C4A3$ therefore does not have anyimpact on the density of the cementitious compositions according to theinvention.

5/Cross-Pollution

As explained hereinabove in point I.6b, the effect of the contaminationof a Portland cement by a cement according to the invention, or of thecontamination of a cement according to the invention by a Portlandcement was evaluated thanks to the Anton Paar viscometer.

Recall that the corresponding gelling time is measured at the moment ofthe change in the slope of the curve (representing the passage of thethickening phase to the setting phase), and the setting time whichcorresponds to the duration that elapses between the formation of thecementitious composition and the moment when the torque reaches 4 mN.m.

For this measurement, the cementitious compositions are prepared asfollows: 100 g of cement is mixed with 44 g of water (i.e. awater/cement ratio of 0.44), using a Rayneri Turbotest mixer, for 15seconds at 1000 revolutions per minute, then for 120 seconds at 3300revolutions per minute.

Table 33 hereinbelow shows the results obtained.

TABLE 33 Phase C4A3$ in the mixture Time measured Cements usedCement3bis + 20° C. CementRef Cement3bis CSA CSA Gelling Setting (%) (%)(%) (%) (min) (min) 25 69 6 8% 240 280 25 75 0 4% 190 260

The cement CSA corresponds to a conventional sulfocalcium aluminatecement that can be found off the shelf.

This can be for example cement KTS 100 marketed by the company PolarBear, having a Blaine specific surface area of 4900 cm²/g. Thiscommercial cement comprises about 55% of phase C4A3$, by weight withrespect to the total weight of the cement.

The adding of sulfocalcium aluminate cement makes it possible tointroduce a given quantity of phase C4A3$ in the cementitiouscomposition and to assess the effect of this phase on the pollution of aPortland cement by a cement according to the invention and inversely.

Here, the mixture of cement Cement3bis according to the invention and ofcement CSA comprises about 8% of phase C4A3$, by weight with respect tothe total weight of said cement mixture. This mixture of cementsundergoes a pollution by the Portland cement of about 25%, or pollutes aPortland cement, by about 25%.

When the mixture of cement is polluted by Portland cement, it is notedthat the gelling and setting times are clearly longer and pass from 190minutes and 260 minutes to 240 minutes and 280 minutes.

Thus, the increase in the minority phase C4A3$ makes it possible tofurther decrease the effect of the pollution of a cement according tothe invention by a Portland cement.

Consequently, it is not necessary to clean the installations between ause of a cement according to the invention and a use of a Portlandcement.

1-11. (canceled)
 12. Calcium aluminate cement, comprising a calciumaluminate with a first crystallised mineralogical phase of calciumdialuminate CA2 comprising one calcium oxide CaO for two aluminiumoxides Al₂O₃ and/or a second crystallised mineralogical phase ofdicalcium alumina silicate C2AS comprising two calcium oxides CaO forone aluminium oxide Al₂O₃ and one silicon dioxide SiO₂, wherein the massfraction of all of said first and second mineralogical phases in saidcalcium aluminate is greater than or equal to 80%.
 13. The calciumaluminate cement according to claim 12, wherein said calcium aluminatealso comprises an amorphous portion, of which the mass fraction in saidcalcium aluminate is less than or equal to 20%.
 14. The calciumaluminate cement according to claim 12, wherein said calcium aluminatefurther comprises a third crystallised mineralogical phase ofmonocalcium aluminate CA comprising one calcium oxide CaO for onealuminium oxide Al₂O₃ and/or a fourth crystallised mineralogical phaseof hexa-calcium aluminate CA6 comprising one calcium oxide CaO for sixaluminium oxides Al₂O₃, the mass fraction of all of the third and fourthmineralogical phases in said calcium aluminate being less than or equalto 20%.
 15. The calcium aluminate cement according to claim 12, whereinsaid calcium aluminate further comprises an additional mineralogicalphase of sulfocalcium aluminate C4A3$ comprising four calcium oxides CaOfor three aluminium oxides Al₂O₃ and one sulphur oxide SO₃.
 16. Thecalcium aluminate cement, according to claim 12, comprising, by weightwith respect to the total weight of said calcium aluminate: 0% to 5% ofan iron oxide Fe₂O₃, 0% to 5% of a titanium oxide TiO₂, 0% to 5% of asulphur oxide SO₃, 0% to 5% of a magnesium oxide MgO, 0% to 2% ofalkaline compounds.
 17. The calcium aluminate cement according to claim12, having the form of a powder that has a Blaine specific surface areameasured according to standard NF-EN-196-6 ranging between 2200 squarecentimetres per gram and 4500 square centimetres per gram.
 18. Thecalcium aluminate cement according to claim 12, comprising, by weightwith respect to the total weight of said calcium aluminate: 50% to 60%of first crystallised mineralogical phase CA2, 26% to 32% of secondcrystallised mineralogical phase C2AS, 2.5% to 3.5% of thirdcrystallised mineralogical phase CA, 0.5% to 1.5% of a fifthcrystallised mineralogical phase of tetracalcium ferro-aluminate C4AF,10% to 15% of additional crystallised mineralogical phases.
 19. Thecalcium aluminate cement according to claim 12, comprising 0.5% to 15%of additional mineralogical phase of sulfocalcium aluminate C4A3$ byweight with respect to the total weight of said calcium aluminate. 20.Cementitious composition comprising at least the calcium aluminatecement of claim 12 mixed with water.
 21. A method for utilizing cementbased on the calcium aluminate cement of claim 12, comprising steps of:a) realizing a cementitious composition by mixing at least said calciumaluminate cement with water, b) setting said cementitious composition inplace, c) heating said cementitious composition to a temperature rangingbetween 50° C. and 300° C., in such a way as to favour the setting ofthe cementitious composition.
 22. The method of claim 21, wherein, inthe step a), the cementitious composition has the form of an aqueoussuspension, and according to which in the step b), the cementitiouscomposition is placed in an oil drilling well.
 23. The calcium aluminatecement according to claim 12, having the form of a powder that has aBlaine specific surface area measured according to standard NF-EN-196-6ranging between 2900 and 3900 square centimetres per gram.
 24. A methodfor utilizing cement based on the calcium aluminate cement of claim 12,comprising steps of: a) realizing a cementitious composition by mixingat least said calcium aluminate cement with water, b) setting saidcementitious composition in place, c) heating said cementitiouscomposition to a temperature ranging between 80° C. and 280° C., in sucha way as to favour the setting of the cementitious composition.
 25. Thecementitious composition of claim 20, further comprising at least onecementitious addition selected from a group consisting of: fly ash,granulated blast furnace slag, a silica flour, a silica fume, ametakaolin, granulates, fine limestone, sand, and adjuvants.
 26. Thecementitious composition of claim 20, further comprising granulatedblast furnace slag.
 27. The cementitious composition of claim 20,further comprising silica flour.
 28. The cementitious composition ofclaim 20, further comprising silica fume.
 29. The cementitiouscomposition of claim 20, further comprising metakaolin.
 30. Thecementitious composition of claim 20, further comprising quartzgranulates .
 31. The cementitious composition of claim 20, furthercomprising fine limestone.